Transition metal complex ligand and olefin polymerization catalyst containing transition metal complex

ABSTRACT

The invention provides a transition metal complex of formula (3) below: 
     
       
         
         
             
             
         
       
         
         
           
             wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are the same or different and each independently represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); R 5  represents a hydrogen atom, a fluorine atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); X 1  represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); L represents a balancing counter ion or neutral ligand similar to X 1  that is bonding or coordinating to metal M; and q represents an integer of 0 or 1, and 
             G 20  represents any one of G 21  to G 26  below: 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             where A 1  represents an element of Group 15 of the periodic table, wherein A 1  in G 23  represents an anion of an element of Group 15 of the periodic table, and A 1  in G 21  represents a nitrogen atom; 
             R 9 , R 14 , R 12 , R 13 , R 19 , R 20 , R 10 , R 11 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21  and R 22  each independently represents, 
             a hydrogen atom; or 
             a substituted or unsubstituted alkyl groups having 1 to 10 carbon atom(s), and 
             the line linking M and R 20  represents that M is coordinated or linked to an element of Group 15 or 16 of the periodic table or to a fluorine atom constituting R 20 .

TECHNICAL FIELD

The invention relates to a transition metal complex, a ligand and anolefin polymerization catalyst, and a production method of an olefinpolymer.

BACKGROUND ART

Conventionally, it has been reported to use a reaction product of anorganic compound having two hydroxyl groups and phosphine (for example,2,2′-(phenylphosphide)bis(6-tert-butyl-4-methylphenoxide)(tetrahydrofuran)titaniumdichloride) for production of olefin polymers (for example JapanesePatent Application Laid-Open (JP-A) No. 10-218922).

DISCLOSURE OF THE INVENTION

The transition metal complex having the ligand of the invention isuseful as a component of an olefin polymerization catalyst. The catalysthas a good polymerization activity and can be used for production ofhigh molecular weight olefin polymers.

The present invention provides:

1. a phosphine compound of formula (1):

wherein R¹, R², R³, R⁴, R⁶, R⁷ and R⁸ are the same or different, andindependently represent;

a hydrogen atom,

a halogen atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

a silyl group substituted with a substituted or unsubstitutedhydrocarbon having 1 to 20 carbon atom(s), a substituted orunsubstituted alkoxy group having 1 to 10 carbon atom(s),

a substituted or unsubstituted aralkyloxy group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryloxy group having 6 to 20 carbonatoms, or

an amino group disubstituted with hydrocarbons having 1 to 20 carbonatom(s);

R⁵ represents,

a hydrogen atom,

a fluorine atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

a silyl group substituted with a substituted or unsubstitutedhydrocarbon having 1 to 20 carbon atom(s);

G¹ represents a hydrogen atom or a protective group of hydroxyl group;

G² represents any one of G²¹ to G²⁶ below;

wherein A¹ represents an element of Group 15 of the periodic table, andA² represents an element of Group 16 of the periodic table, wherein A¹in G²¹ represents a nitrogen atom;

R⁹ and R¹⁴ each represents

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

a group of formula:R⁹⁰—N—R⁹¹

wherein R⁹⁰ and R⁹¹ are the same or different, and represent

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

a cyclic structure by being linked together;

R¹², R¹³, R¹⁹ and R²⁰ each independently represents

a substituted or unsubstituted alkyl group 1 to 10,

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

R¹² and R¹³, and R¹⁹ and R²⁰, each independently, are linked togetherand represent cyclic structure;

R¹⁰, R¹¹, R¹⁵, R¹⁶, R²¹ and R²² each independently represents

A hydrogen atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

R¹⁷ and R¹⁸ are the same or different, and represent,

a hydrogen atom,

a halogen atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or

a substituted or unsubstituted aryl group having 6 to 20 carbon atom(s);and

m represents an integer of 0 or 1;

2. a production method of a phosphine compound of formula (21B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²¹ and G¹⁰ are as definedbelow, which comprises reacting

a phosphine carbonyl compound of formula (21C):

wherein G¹⁰ represents a hydrogen atom, or a protective group of ahydroxyl group selected from an alkyl group having a secondary ortertiary carbon atom linked to an oxygen atom of phenol, or a C1 to C2alkyl group substituted with a substituted or unsubstituted alkoxygroup, and

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R²¹ are the same as defined above,with an organic compound of formula (21F):R⁹NH₂  (21F)

wherein R⁹ is as defined above;

3. a production method of a phosphine compound of formula 21A:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are as described above,and A¹ represents a nitrogen atom, which comprises

reacting the phosphine compound of formula 21B above, wherein G¹⁰ is aprotective group of hydroxyl group selected from an alkyl group having asecondary or tertiary carbon atom linked to an oxygen atom of phenol ora C1 or C2 alkyl group substituted with a substituted or unsubstitutedalkoxy group, with an acid;

4. a production method of the phosphine compound of formula (22A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², R¹³ and A¹ are asdescribed above, which comprises reacting

-   -   a phosphine compound of formula (22B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², R¹³ and A¹ arethe same as described above, and G¹¹ represents a protective group ofhydroxyl group selected from an alkyl group having a secondary ortertiary carbon atom linked to an oxygen atom of phenol, or C1 to C2alkyl groups substituted with a substituted or unsubstituted alkoxygroup, with an acid;

5. a production method of a phosphine compound of formula (22B) above,which comprises reacting a phosphine dihalide compound of formula (22C):

wherein A, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³ and A¹ are as defined above,and X² represents a halogen atom,

-   -   with a metal aryl compound of formula (22D);

wherein R¹, R², R³, R⁴ and G¹¹ are the same as above, and D representsan alkali metal or J-X³, where J represents an alkaline earth metal andX³ represents a halogen atom;

6. a production method of a phosphine compound of formula (22B) abovewhich comprises reacting

a phosphine halide compound of formula (25C):

wherein R¹, R², R³, R⁴ and G¹¹ are as described above, and X² representsa halogen atom, with a metal aryl compound of formula (22E):

wherein A, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, A¹ and D are asdescribed above;

7. a production method of a phosphine compound of formula (23B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, A¹ and R²² are as describedabove, which comprises reacting a phosphine compound of formula (23C):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, G¹¹ and R²² are asdescribed above, with a metal hydride compound;

8. a production method of a phosphine compound of formula (23A):

wherein, A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, A¹ and R²² are asdescribed above,

which comprises reacting

a phosphine compound of formula (23B) with an acid;

9. a production method of a phosphine compound of formula (24A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶ and A² are as describedabove,

which comprises reacting a phosphine compound of formula (24B):

wherein, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, A² and G¹¹ are asdescribed above, with an acid;

10. a production method of a phosphine compound of formula (24B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, A² and G¹¹ are asdescribed above,

which comprises reacting

a phosphine compound of formula (24C):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, A² and G¹¹ are as describedabove,

with a metal hydride compound or a metal aryl compound of formula (24D);R¹⁶—Y  (24D)

wherein R¹⁶ and Y represent an alkali metal, or

J-X³, wherein J represents an alkali earth metal and X³ represents ahalogen atom;

11. a production method of a phosphine compound of formula (25A):

wherein, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸ and m are as describedabove,

which comprises reacting

a phosphine compound of formula (25B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸, G¹¹ and m are asdescribed above,

with an acid;

12. a production method of a phosphine compound of formula (25B) above,which comprises reacting

a phosphine halide compound of formula (25C):

wherein R¹, R², R³, R⁴ and are G¹¹ are as above, and X² represented ahalogen atom,

with a metal aryl compound of formula (25D);

wherein R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, D and m are as described above;

13. a production method of a phosphine compound of formula (25B) above,which comprises reacting

a halo-phosphine compound of formula (25E):

wherein R⁵, R⁶, R⁷, R⁸, R⁹⁵, R⁹⁶ and m are as described above, and X²represents a halogen atom,

with a metal aryl compound of formula (25F);

wherein R¹, R², R³, R⁴, G¹¹ and D are as described above;

14. a production method of a phosphine compound of formula (26A):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and A¹ are asdescribed above,

which comprises reacting

a phosphine compound of formula (26B):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and G¹¹ are asdescribed above,

with an acid;

15. a production method of a phosphine compound of formula (26B) above,which comprises reacting

a halo-phosphine compound of formula (26C):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and A¹ are as described above, and X²represents a halogen atom,

with a metal aryl compound of formula (26D):

wherein R¹, R², R³, R⁴, D and G¹ (preferably G¹¹) are as describedabove;

16. a production method of a phosphine compound of formula (26B) above,which comprises reacting

an aryl halogenated phosphorous compound of formula (26E):

wherein R¹, R², R³, R⁴ and G¹¹ are as described above, and X² representsa halogen atom,

with a metal aryl compound of formula (26F):

wherein A¹, R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and D are as described above;

17. a production method of a transition metal complex of formula (3):

wherein M, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, X¹ and L are as describedbelow,

q represents an integer of 0 or 1;

G²⁰ represents any one of G²¹ to G²⁶ below;

wherein A¹ represents an element of Group 15 of the periodic table, A¹in G²³ represents an anion of an element of Group 15 of the periodictable, A² represents an anion of an element of Group 16 of the periodictable, and A¹ in G²¹ represents a nitrogen atom;

R⁹ and R¹⁴ each represents,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

a group of formula:R⁹⁰—N—R⁹¹,

wherein R⁹⁰ and R⁹⁰ are the same or different, and represent

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or

a cyclic structure being linked together;

R¹², R¹³, R¹⁹ and R²⁰ each independently represents,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;or

R¹² and R¹³, and R¹⁹ and R²⁰ each independently represent a cyclic groupbeing linked together;

R¹⁰, R¹¹, R¹⁵, R¹⁶, R²¹ and R²² each independently represents,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

R¹⁷ and R¹⁸ are the same or different, and each represents

a hydrogen atom,

a halogen atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

m represents an integer of 0 or 1; and

the line linking M and G²⁰ means that M is linked or coordinated to anelement of Group 15 or 16 of the periodic table or to a fluorine atomconstituting G²⁰,

which comprises reacting

a phosphine compound of formula (2):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as described above, andG¹⁰ represents

a hydrogen atom, or a protective group of hydroxyl group selected froman alkyl group having a secondary or tertiary carbon atom linked to anoxygen atom of phenol or a C1 to C2 alkyl group substituted with asubstituted or unsubstituted alkoxy group,

with a transition metal compound of formula (4):MX¹ ₃LL¹p  (4)

wherein

M represents an element of Group 4 of the periodic table;

X¹ represents,

a hydrogen atom,

a halogen atom,

a substituted or unsubstituted alkyl group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

a substituted or unsubstituted alkoxy group having 1 to 10 carbonatom(s),

a substituted or unsubstituted aralkyloxy group having 7 to 20 carbonatoms,

a substituted or unsubstituted aryloxy group having 6 to 20 carbonatoms, or

an amino group disubstituted with a hydrocarbon having 2 to 20 carbonatoms:

L represents a balancing counter ion or neutral ligand, being an atom ora group similar to X¹, and is bonding or coordinating to metal M, L¹represents a neutral ligand, and p represents an integer of 0 to 2;

18. a production method of the transition metal complex of formula (3)above,

which comprises reacting

a phosphine compound of formula (5):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, G¹¹ and G² are as describedabove,

with the transition metal compound of formula (4) above;

19. the transition metal complex of formula (3);

20. an olefin polymerization catalyst prepared by combining thetransition metal compound of formula (3) and the following compound A,and optionally compound B;

compound A: any one of A1 to A3 below, or a mixture of at least two ofthem;

A1: an organic aluminum compound of formula (E1)_(a)Al(Z)_((3-a));

A2: a cyclic aluminoxane having a structure represented by[—Al(E2)-O-]_(b); and

A3: a linear aluminoxane having a structure represented by(E3)[—Al(E3)-O—]_(c)Al(E3)₂;

wherein, E1 to E3 are the same or different and are hydrocarbons having1 to 8 carbon atom(s); Z is the same or different and represents ahydrogen atom or a halogen atom; a represents 1, 2 or 3; b represents aninteger of 2 or more; and c represents an integer of 1 or more; and

compound B: any one of B1 to B3 below, or a mixture of at least two ofthem;

B1: a boron compound of formula BQ¹Q²Q³;

B2: a boron compound of formula Z⁺(BQ¹Q²Q³Q⁴); and

B3: a boron compound of formula (L-H)⁺(BQ¹Q²Q³Q⁴);

wherein B is a boron atom in a trivalent atomic valance state, Q¹ to Q⁴are the same or different, and represent a halogen atom, a hydrocarbonhaving 1 to 20 carbon atom(s), a halogenated hydrocarbon having 1 to 20carbon atom(s), an alkoxy group having 1 to 20 carbon atom(s), a silylgroup substituted with a hydrocarbon having 1 to 20 carbon atom(s), oran amino group disubstituted with hydrocarbons having 1 to 20 carbonatom(s); and

21. a production method of an olefin polymer for polymerizing an olefinusing the olefin polymerization catalyst above.

BEST MODE FOR CARRYING OUT THE INVENTION

Substituents of the phosphine compound of formula (1) will be describedbelow.

Specific examples of the halogen atom represented by R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R¹⁷ or R¹⁸ include a fluorine atom, a chlorine atom, abromine atom and an iodine atom, and the chlorine atom is preferable asthe halogen atoms of R¹, R², R³, R⁴, R⁶, R⁷ and R⁸, and the fluorineatom is preferable as the halogen atoms of R¹⁷ and R¹⁸.

Specific examples of the unsubstituted C1 to C10 alkyl groupsrepresented by R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R⁹⁰ or R⁹¹ include methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,neopentyl, amyl, n-hexyl, n-octyl and n-decyl groups. Examples of thesubstituted C1 to C10 alkyl groups include the C1 to C10 alkyl groupssubstituted with a halogen atom, an alkoxy group, an aryloxy group, ahydrocarbon-substituted amino group or a silyl group substituted with ahydrocarbon, and specific examples thereof include a fluoromethyl group,a difluoroethyl group, a trifluoromethyl group, a fluoroethyl group, adifluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, apentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group,a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group,a perfluorodecyl group, a trichloromethyl group, a methoxymethyl group,a phenoxymethyl group, a diaminomethyl group and a trimethylsilylmethylgroup.

Among the alkyl groups that may be substituted having 1 to 10 carbonatom(s), the methyl, ethyl, isopropyl, tert-butyl and amyl groups arepreferable, and the methyl and tert-butyl groups are more preferable.

Examples of unsubstituted C7 to C20 aralkyl groups represented by R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R⁹⁰ and R⁹¹ include benzyl, naphthylmethyl,anthracenylmethyl and diphenylmethyl groups; examples of the substitutedC7 to C20 aralkyl groups include those substituted with a halogen atom,an alkyl group, an alkoxy group, an aryloxy group or ahydrocarbon-substituted amino group, or with a silyl group substitutedwith a hydrocarbon; and specific examples of the substituted orunsubstituted aralkyl group having 7 to 20 carbon atoms include(2-methylphenyl)methyl group, (3-methylphenyl)methyl group,(4-methylphenyl)methyl group, (2,3-dimethylphenyl)methyl group,(2,4-dimethylphenyl)methyl group, (2,5-dimethylphenyl)methyl group,(2,6-dimethylphenyl)methyl group, (3,4-dimethylphenyl)methyl group,(2,3,4-trimethylphenyl)methyl group, (2,3,5-trimethylphenyl)methylgroup, (2,3,6-trimethylphenyl)methyl group,(3,4,5-trimethylphenyl)methyl group, (2,4,6-trimethylphenyl)methylgroup, (2,3,4,5-tetramethylphenyl)methyl group,(2,3,4,6-tetramethylphenyl)methyl group,(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methylgroup, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,(sec-butylphenyl)methyl group, (tert-butylphenyl)methyl group,(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,(n-hexylphenyl)methyl group, (n-octylphenyl)methyl group,(n-decylphenyl)methyl group, (n-dodecylphenyl)methyl group,(fluorophenyl)methyl group, (difluorophenyl)methyl group,(pentafluorophenyl)methyl group, (chlorophenyl)methyl group,(phenoxyphenyl)methyl group, (dimethylaminophenyl)methyl group and(trimethylsilylphenyl)methyl group. The benzyl group is preferable asthe substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms.

Examples of unsubstituted C6 to C20 aryl groups represented by R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, R²², R⁹⁰ or R⁹¹ include phenyl, naphthyl and anthracenylgroups, and examples of substituted C6 to C20 aryl groups include thosesubstituted with a halogen atom, an alkyl group, an alkoxy group, anaryloxy group and a hydrocarbon-substituted amino group, or with a silylgroup substituted with a hydrocarbon. Specific examples thereof include2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl,3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl,2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl,2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl,2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl,n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl,tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl,n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl,2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluorophenyl,pentafluorophenyl, 4-chlorophenyl, 2-methoxyphenyl, 3-methoxyphenyl,4-methoxyphenyl, 4-phenoxyphenyl, 4-dimethylaminophenyl and4-trimethylsilylphenyl groups. Preferred substituted or unsubstituted C6to C20 aryl group is the phenyl group.

Examples of cyclic structures formed by linking R¹² and R¹³ togetherinclude C4 to C6 cyclic alkylene groups such as tetramethylene,pentamethylene and hexamethylene groups. Examples of cyclic structuresformed by linking R¹⁹ and R²⁰ and R⁹⁰ and R⁹¹ together include the samegroups. Examples of cyclic structures formed by linking R⁹⁰ and R⁹¹together include 1-pyrolyl group.

Examples of the hydrocarbon of the silyl group substituted withunsubstituted C1 to C20 hydrocarbons represented by R¹, R², R³, R⁴, R⁵,R⁶, R⁷ or R⁸ include alkyl groups having 1 to 10 carbon atom(s) such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, cyclohexyl, n-octyl and n-dodecylgroups; and C6 to C20 aryl groups such as phenyl, tolyl, xylyl, naphthyland anthracenyl groups. Examples of the silyl group substituted withthese C1 to C20 hydrocarbons include monosubstituted silyl groups suchas methylsilyl, ethylsilyl, phenylsilyl group; disubstituted silylgroups such as dimethylsilyl, diethylsilyl or diphenylsilyl group; andtri-substituted silyl groups such as trimethylsilyl, triethylsilyl,tri-n-propylsilyl, tri-isopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyldimethylsilyl, tri-n-pentylsilyl, tri-n-pentylsilyl,tri-n-hexylsilyl, tricyclohexylsilyl or triphenylsilyl group. Examplesof the preferable silyl group substituted with substituted orunsubstituted C1 to C20 hydrocarbons include trimethylsilyl,tert-butyldimethyl and triphenylsilyl groups. Examples of the silylgroup substituted with substituted C1 to C20 hydrocarbons include allthe silyl groups substituted with such a hydrocarbon that is substitutedwith a halogen atom, for example, a fluorine atom.

Specific examples of unsubstituted C1 to C10 alkoxy groups representedby R¹, R², R³, R⁴, R⁶, R⁷ or R⁸ include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy and n-decyloxy groups.Examples of substituted C1 to C10 alkoxy groups include C1 to C10 alkoxygroups substituted with a halogen atom, an alkoxy group, an aryloxygroup, a hydrocarbon-substituted amino group, or with a silyl groupsubstituted with a hydrocarbon.

Specific examples of the substituted alkoxy group include fluoromethoxy,difluoromethyoxy, trifluoromethoxy, fluoroethoxy, difluoroethoxy,trifluoroethoxy, tetrafluoroethoxy, pantafluoroethoxy,perfluororpropoxy, perfluorobutyloxy, perfluoropentyloxy,perfluorohexyloxy, perfluorooctylcoxy, perfluorodecyloxy,trichloromethyloxy, methoxymethoxy, phenoxymethoxy, dimethylaminomethoxyand trimethylsilylmethoxy groups. Preferred are substituted orunsubstituted C1 to C10 alkoxy groups such as methoxy, ethoxy,tert-butoxy group or the like.

Examples of unsubstituted C7 to C20 aralkyloxy groups represented by R¹,R², R³, R⁴, R⁷ or R⁸ include benzyloxy, naphthylmethoxy,anthracenylmethoxy and diphenylmethoxy groups.

Examples of the substituted C7 to C20 aralkyloxy group include thosesubstituted with a halogen atom, an alkyl group, an alkoxy group, anaryloxy group, a hydrocarbon-substituted amino group, or with a silylgroup substituted with a hydrocarbon. Specific examples thereof include(2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group,(4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group,(2,4-dimethylphenyl)methoxy group, (2,5-dimethylphenyl)methoxy group,(2,6-dimethylphenyl)methoxy group, (3,4-dimethylphenyl)methoxy group,(2,3,4-trimethylphenyl)methoxy group, (2,3,5-trimethylphenyl)methoxygroup, (2,3,6-trimethylphenyl)methoxy group,(3,4,5-trimethylphenyl)methoxy group, (2,4,6-trimethylphenyl)methoxygroup, (2,3,4,5-tetramethylphenyl)methoxy group,(2,3,4,6-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, (ethylphenyl)methoxy group, (n-propylphenyl)methoxy group,(isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group,(sec-butylphenyl)methoxy group, (tert-butylphenyl)methoxy group,(n-pentylphenyl)methoxy group, (neopentylphenyl)methoxy group,(n-hexylphenyl)methoxy group, (n-octylphenyl)methoxy group,(n-decylphenyl)methoxy group, (n-dodecylphenyl)methoxy group,(fluorophenyl)methyl group, (difluorophenyl)methyl group,(pentafluorophenyl)methyl group, (chlorophenyl)methyl group,(methoxyphenyl)methyl group, (phenoxyphenyl)methyl group,(dimethylaminophenyl)methyl group and (trimethylsilylphenyl)methylgroup. Preferable examples of the substituted or unsubstituted C7 to C20aralkyloxy groups include benzyloxy group and the like.

Examples of the unsubstituted or substituted C6 to C20 aryloxy grouprepresented by R¹, R², R³, R⁴, R⁷ or R⁸ include phenoxy, naphthoxy andanthracenoxy groups.

Examples of the substituted C6 to C20 aryloxy group include thosesubstituted with a halogen atom, an alkyl group, al alkoxy group, anaryloxy group, a hydrocarbon-substituted amino group, or with a silylgroup substituted with a hydrocarbon.

Specific examples thereof include 2-methylphenoxy group, 3-methylphenoxygroup, 4-methylphenoxy group, 2,3-dimethylphenoxy group,2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group,2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group,3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group,2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group,3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group,2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group,pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group,isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group,tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group,n-decylphenoxy group, n-tetradecylphenoxy group, 2-fluorophenoxy group,3-fluorophenoxy group, 4-fluorophenoxy group, 3,5-difluorophenoxy group,pentafluorophenoxy group, 4-chlorophenoxy group, 2-methoxyhenoxy group,3-methoxyhenoxy group, 4-methoxyphenoxy group, 4-phenoxyphenoxy group,4-dimethylaminophenoxy group and 4-trimethylsilylphenoxy group.Preferable examples of the substituted or unsubstituted C7 to C20aryloxy groups include the phenoxy group and the like.

The amino group disubstituted with the unsubstituted C1 to C20hydrocarbon, represented by R¹, R², R³, R⁴, R⁶, R⁷ or R⁸, is an aminogroup substituted with two hydrocarbons, wherein examples of thehydrocarbon include C1 to C10 alkyl groups such as methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl,neopentyl, amyl, n-hexyl, cyclohexyl, n-octyl or n-decyl; and C6 to C20aryl groups such as phenyl, tolyl, xylyl, naphthyl or anthracenyl group.Examples of the amino group substituted with these C1 to C20hydrocarbons include dimethylamino group, diethylamino group,di-n-propylamino group, di-isopropylamino group, di-n-butylamino group,di-sec-butylamino group, di-tert-butylamino group, di-isobutylaminogroup, tert-butylisopropylamino group, di-n-hexylamino group,di-n-octylamino group, di-n-decylamino group and diphenylamino group,and preferable examples include dimethylamino group and diethylaminogroup.

Examples of the protective group represented by G¹ include protectivegroups of hydroxyl group selected from alkyl groups having a secondaryor tertiary carbon atom linked to an oxygen atom of phenol, or C1 to C2alkyl groups substituted with a substituted or unsubstituted alkoxygroup, or a substituted or unsubstituted C7 to C20 aralkyl groups.

Examples of the alkyl group having secondary or tertiary carbon atomlinked to the oxygen atom of phenol include isopropyl, tert-butyl andsec-butyl groups.

Examples of the protective group of the hydroxyl group selected from C1to C2 alkyl groups substituted with the substituted or unsubstitutedalkoxy group include methoxymethyl, ethoxyethyl, methoxyethoxymethyltrimethylsilylethoxymethyl or 1-ethoxyethyl group.

Examples of the substituted or unsubstituted C7 to C20 aralkyl groupsinclude those as described above. Examples of the preferable protectivegroup include the protective group of the hydroxyl group, as shown byG¹¹, selected from alkyl groups having the secondary or tertiary carbonatom linked to the oxygen atom of phenol, and C1 to C2 alkyl groupssubstituted with a substituted or unsubstituted alkoxy group, andexamples of the more preferable protective group include methoxymethyl,ethoxyethyl, methoxyethoxymethyl, trimethylsilylethoxymethyl or1-ethoxyethyl group that is a protective group of the hydroxyl groupselected from C1 to C2 alkyl groups substituted with substituted orunsubstituted alkoxy group.

In G²¹, G²², G²³, G^(23′) and G²⁶ of G², the 15th group of the periodictable represented by A¹ is preferably a nitrogen atom, and the 16thgroup of the periodic table represented by A² in G²⁴ and G^(24′) ispreferably an oxygen atom.

Examples of the compound in which G¹ represents a hydrogen atom informula (1) include the compounds of formulae 21A, 22A, 23A, 24A, 25Aand 26A. Examples of the compound representing G¹¹ in which G¹represents a group other than hydrogen include the compounds of formulae21B, 22B, 23B, 24B and 25B.

The compound of formula (21A) can be produced by reacting the compoundof formula (21B) with the organic compound of formula 21F.

The compound of formula (21A) can be obtained by reacting the compoundof formula (21B) with an acid, wherein the compound of formula (21B) isa protective group of the hydroxyl group selected from alkyl groupshaving a secondary or tertiary carbon atom linked to the oxygen atom ofphenol, and C1 to C2 alkyl groups substituted with a substituted orunsubstituted alkoxy group. Examples of the production method of thecompounds of formulae (21B) and (21A), in which G¹¹ is the protectivegroup of the hydroxyl group selected from alkyl groups having asecondary or tertiary carbon atom linked to the oxygen atom of phenol,and C1 to C2 alkyl groups substituted with a substituted orunsubstituted alkoxy group, will be described below. The compound offormula (22A), (23A), (24A) or (25A) may be also produced in a similarmanner above by a reaction with the corresponding compound of formula(22B), (23B), (24B) or (25B), respectively.

An example of the acid in this reaction is a Bronsted acid (for example,inorganic acids), and detailed examples thereof include halogenatedhydrogen such as hydrogen chloride, hydrogen bromide and hydrogeniodide, and sulfuric acid, preferably hydrogen chloride. The compound offormula (25A) may be obtained from the compound of formula (22A) bydeprotection with an acid as a salt of Bronsted acid (for example, saltsof inorganic acids or halogenated hydrogen) such as phosphine, amine andimine salts.

Hydrogen chloride gas may be used as the hydrogen chloride used in thereaction above, or hydrogen chloride may be generated from an acidchloride and an alcohol in the reaction system.

The reaction is usually carried out in a solvent inert to the reaction.Examples of the solvent available are aprotic solvents includingaromatic hydrocarbon solvents such as benzene or toluene; aliphatichydrocarbon solvents such as hexane or heptane; ether solvents such asdiethyl ether, tetrahydrofuran or 1,4-dioxane; polar solvents such asacetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutylketone, cyclohexanone or ethyl acetate; and halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene or dichlorobenzene. Thesesolvents may be used alone or as a mixture of at least two of them, andthe amount thereof is usually in the range of 1 to 200 parts by weight,preferably 3 to 50 parts by weight per part by weight of the phosphinecompound of formula (21B).

The reaction temperature is usually in the range of −100° C. or more tothe boiling point or less of the solvent, preferably about −80 to 100°C.

The phosphine compound of formula (22A) can be obtained by aconventional method for obtaining a product from a reaction mixture, forexample by removing the solvent by evaporation.

The following compounds are the specific examples of the phosphinecompounds of formula (21A):

Specific examples of the phosphine compounds of formula (21B) include,for example, the following compounds:

The compound of formula (21A), which corresponds to compounds of formula(1) wherein G¹ has the structure of G²¹ can be produced by reacting thephosphine carbonyl compound of formula (21C) with the organic compoundof formula (21F).

While the reaction molar ratio between the phosphine carbonyl compoundof formula 21C and the organic compound of formula (21F) is notparticularly restricted, the ratio is preferably in the range of 1:0.1to 1:10, more preferably in the range of 1:0.5 to 1:5.

The reaction is usually performed in an inert solvent. Examples of thesesolvents include, for example, aprotic solvents including aromatichydrocarbon solvents such as benzene or toluene; aliphatic hydrocarbonsolvents such as hexane or heptane; ether solvents such as diethylether, tetrahydrofuran or 1,4-dioxane; polar solvents such asacetonitrile, propionitrile, acetone, diethyl ketone, methyl isopropylketone, cyclohexanone or ethyl acetate; and hydrogenated solvents suchas dichloromethane, dichloroethane, chlorobenzene or dichlorobenzene;and protonic solvents such as methanol, ethanol, isopropanol or butanol.These solvents may be used alone or as a mixture of at least two ofthem. The amount of these solvents is usually 1 to 200 parts by weight,preferably 3 to 50 parts by weight, per part by weight of the carbonylcompound of formula (7).

The reaction temperature is usually in the range of from −100° C. ormore to the boiling point or below of the solvent, preferably about −80to 100° C. The phosphine compound of formula (21C), wherein G¹ in theformula denotes a hydrogen atom can be obtained from the reactionmixture by a conventional method, for example, by removing the solventby evaporation. Specific examples of the phosphine carbonyl compound offormula (21C) include, for example, the following compounds:

Specific examples of the organic compound of formula (21F) includemethylamine, ethylamine, propylamine, butylamine, isobutylamine,tert-butylamine, pentylamine, hexylamine, aniline, 2-methylaniline,4-methylaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline,pentafluoroaniline, aminopiperidine, aminopyrrole and the like. Specificexamples of the carbonyl compound of formula (21C) include the followingcompounds:

The phosphine compound of formula (21C) can be synthesized by thefollowing reaction route:

In the scheme, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R²¹ and G¹¹ have the samemeanings as described above, and R⁹³ denotes a substituted orunsubstituted alkyl or aralkyl group, or a cyclic alkylene group bylinking together.

In the compound of formula (22A), which corresponds to the compound offormula (1), wherein G¹ has the structure of G²², and A¹ is P, can beproduced by deprotecting the compound of formula (22B) wherein A¹ is P,in a similar manner as the compound wherein A¹ is N as explained above.The compound of formula (22B) wherein A¹ is P, can be synthesized fromthe compound of formula (22E) wherein which A¹ is P, in a similar manneras the compound wherein A¹ is N. The compound of formula (22E) whereinA¹ is P, can be synthesized from a phosphine-substituted halogenatedaryl as a precursor, for example, by reacting1-(α-chloromethyl)-2-bromobenzene with a mono-substituted phosphine inthe presence of a base as described in Journal of Praktische Chemie(Leipzig), vol. 330, p674, 1988.

Specific examples of the compound of formula (22A), which corresponds tothe compounds of formula (1) wherein G¹ has the structure of G²²include, for example, the following compounds:

Specific examples of the compound of formula (22B), which corresponds tothe compound of formula (1) wherein G² is G²² include, for example, thefollowing compounds:

The phosphine compound of formula (22B) can be synthesized by reactingphosphine dihalide of formula (22C) with the metal aryl compound offormula (22D).

The molar ratio between the phosphine dihalide of formula (22B) and themetal aryl compound of formula (22C) is not particularly restricted, theratio is preferably in the range of 1:2 to 1:5, more preferably in therange of 1:2 to 1:2.5.

Specific examples of the halogen atom represented by X² includefluorine, chlorine, bromine and iodine atoms, and the chlorine atom ispreferable.

Specific examples of the alkali metal and the alkaline earth metalrepresented by D in formula (22D) include lithium, sodium, potassium,magnesium and calcium atoms, and lithium and magnesium atoms arepreferable.

While the reaction is usually carried out in a solvent inert to thereaction, examples of the solvent include aromatic hydrocarbon solventssuch as benzene, toluene or the like, aliphatic hydrocarbon solventssuch as hexane, heptane or the like, and ether solvents such as diethylether, tetrahydrofuran or the like. These solvents may be used alone oras a mixture of at least two of them, and the ratio of use thereof isusually in the range of 1 to 200 parts by weight, preferably in therange of 3 to 50 parts by weight, per part by weight of the metal arylcompound of formula (22D).

The reaction can be usually performed by adding phosphine dihalide offormula (22C) to the metal aryl compound of formula (22D). The reactiontemperature is usually in the range of from −100° C. or more to theboiling temperature of the solvent or less, preferably in the range of−80° C. to 100° C.

The phosphine compound of formula (22B) can be obtained by removinginsolubles by a conventional method such as filtration, and by removingthe solvent by evaporation. The product is purified by silica gel columnchromatography, if necessary.

Phosphine dihalide of formula (22C) is produced by a reaction betweentrihalogenated phosphorous of formula:

P(X²)₃ (X² represents a halogen atom) and a metal aryl compound.

For example, phosphine dihalide may be produced by a reaction betweenthe metal aryl compound of formula (22E) and phosphorous trihalide.

The molar ratio between the metal aryl compound of formula (22E) andphosphorous trihalide that may be used in the reaction is notparticularly restricted, and it is preferably in the range of 1:1 to1:5, more preferably in the range of 1:1 to 1:2.5.

The reaction is usually performed in a solvent inert to the reaction.Examples of the solvent include aromatic hydrocarbon solvents such asbenzene, toluene or the like, aliphatic hydrocarbon solvents such ashexane, heptane or the like, and ether solvents such as diethyl ether,tetrahydrofuran or the like. These solvents may be used alone or as amixture of at least two of them, and the ratio thereof that may be usedis usually in the range of 1 to 200 parts by weight, preferably in therange of 3 to 50 parts by weight, per part by weight of the metal arylcompound of formula (22E).

The reaction can be usually performed by adding phosphorous trihalide tothe metal aryl compound of formula (22E). The reaction temperature isusually in the range from −100° C. or more to the boiling point or lessof the solvent, more preferably in the range of −80° C. to 100° C.

The phosphine dihalide of formula 22C can be obtained from the reactionmixture obtained by a conventional method, for example by removinginsoluble products by filtration followed by removing the solvent byevaporation. The product may be purified by distillation, if necessary.

The metal aryl compound of formula (22D) can be produced by reacting anorganic compound of formula (22F):

wherein R¹, R², R³, R⁴ and G¹¹ each denotes the same meaning asdescribed above, and X represents a hydrogen atom or a halogen atom,with a lithiating agent when X is hydrogen, or with the lithiating agentor magnesium metal, when X is a halogen atom. The molar ratio betweenthe organic compound of formula (22F) and the lithiating agent ormagnesium metal that may be used in the reaction is not particularlyrestricted, and it is preferably in the range of 1:1 to 1:5, morepreferably in the range of 1:1 to 1:2.5. Examples of the lithiatingagent include methyl lithium, n-butyl lithium, s-butyl lithium, t-butyllithium and phenyl lithium, and preferred is n-butyl lithium.

The reaction is usually performed in a solvent inert to the reaction.Examples of the solvent include aromatic hydrocarbon solvents such asbenzene, toluene or the like, aliphatic hydrocarbon solvents such ashexane, heptane or the like, and ether solvents such as diethyl ether,tetrahydrofuran or the like. These solvents may be used alone or as amixture of at least two of them, and the ratio thereof is usually in therange of 1 to 200 parts by weight, preferably in the range of 3 to 50parts by weight, per part by weight of the organic compound of formula(22F). The reaction can be usually performed by adding the lithiatingagent to organic compound of formula (22F). The reaction temperature isusually in the range from −100° C. or more to the boiling point or lessof the solvent, more preferably in the range of −80° C. to 100° C.

Specific examples of phosphine dihalide of formula (22C) include, forexample, the following compounds and those that have bromine or iodineatom in place of the chlorine atom in the illustrated compounds:

Specific examples of the metal aryl compound of formula (22D) include,for example, the following compounds:

Specific examples of the metal aryl compound of formula (22E) include,for example, the following compounds:

Specific examples of the starting material for the compound of formula(22E) include, for example, the following compounds:

The compound in which A¹ is P in the compound of formula (22A) can besynthesized by deprotection the compound of formula (23B) wherein A¹ isP as in the compound in which A¹ is N. The compound of formula (23B)wherein A¹ is P can be synthesized by using the compound of formula(22E) wherein A¹ is P as a starting material. An excess amount of analkali metal reagent may be used in the coupling reaction by suitablyadjusting, if necessary.

The halogenated aryl compound as a precursor of the compound in which A¹is P in formula 22E may be synthesized by a known method described (forexample, Zeitschrift fuer Anorganische Chemie, vol. 494, p55, 1892), forexample by activating 1-(α-bromomethyl)-2-bromobenzene with an alkalimetal, followed by reacting a chlorophosphine compound. Examples of thecompound of formula 23A, which corresponds to the compounds of formula(1) wherein G¹ has the structure of G²³ will be shown below:

Specific examples of haudrogen halide acid salts of the compound offormula (23A) include, for example, the following compounds:

Specific examples of the phosphine compound of formula (1) wherein G¹ isG²³, which corresponds to the compound of formula (23B) include, forexample, the following compounds:

The phosphine compound of formula (23B) where A¹ denotes a nitrogen atomcan be produced by reducing the compound of formula (23C). The reducingreaction can be performed by using a metal hydride compound such assodium borohydride, lithium aluminum hydride or the like, or hydrogenand the like.

The molar ratio between the compound of formula (23C) and metal hydridecompound or hydrogen that may be used in the reaction is notparticularly restricted, and it is preferably in the range of 1:0.1 to1:10, more preferably in the range of 1:0.5 to 1:5.

The reaction is usually performed in an organic solvent. Examples of thesolvent include aprotic solvents including aromatic hydrocarbon solventssuch as benzene, toluene or the like; aliphatic hydrocarbon solventssuch as hexane, heptane or the like; ether solvents such as diethylether, tetrahydrofuran or the like; and halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene or thelike; and protonic solvents such as methanol, ethanol, isopropanol,butanol or the like. These solvents may be used alone or as a mixture ofat least two of them, and the ratio thereof is usually in the range of 1to 200 parts by weight, preferably in the range of 3 to 50 parts byweight, per part by weight of the triaryl compound of formula (23C).

The reaction can be usually performed by adding the metal hydridecompound or hydrogen to the compound of formula (23C). The reactiontemperature is usually in the range from −100° C. or more to the boilingpoint of the solvent or the less, more preferably in the range of −80°C. to 100° C.

The phosphine compound of formula (23B) may be obtained from thereaction mixture obtained by removing the solvent by evaporation. Or,the compound may be purified by silica gel chromatography, if necessary.

Examples of the compound of formula (23C) include the followingcompounds:

Examples of the compound of formula (1) wherein G² is G²⁴ include thefollowing compounds:

Examples of the phosphine compound of formula (1) wherein G² is G²⁴, orthe compound of formula (24B), include, for example, the followingcompounds:

The phosphine compound of formula (24B) is produced by reacting thephosphine compound of formula (24C) with a metal hydride compound or theorganic metal compound of formula (24D), R¹⁶—Y, wherein R¹⁶ and Y are asdescribed above.

The molar ratio between the phosphine compound of formula (24C) and themetal hydride compound or the organic metal compound organic metalcompound of formula (24D) in the reaction is not particularlyrestricted, and the ratio is preferably in the range of 1:0.1 to 1:10,more preferably in the range of 1:0.5 to 1:5.

Examples of the metal hydride compound in the reaction above include,for example, sodium borohydride, potassium borohydride, zincborohydride, sodiumcyanoborohydride, sodium triethylborohydride, lithiumaluminum hydride, diisobutyl aluminum hydride, tri(tert-butoxy)lithiumaluminum hydride and the like.

Examples of the organic metal compound of formula (24D) include, forexample, organic alkali metal compounds including organic lithiumcompounds such as methyl lithium, ethyl lithium, n-butyl lithium,sec-butyl lithium, tert-butyl lithium, lithium trimethylsilyl acetylide,lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyllithium and allyl lithium; and organic alkaline earth metal halide suchas organic magnesium halide including methylbromo magnesium, ethylbromomagnesium, phenylbromo magnesium, tolylbromo magnesium, benzylbromomagnesium or the like.

The reaction above is usually performed in an organic solvent. Examplesof the solvent include, for example, aprotic solvents including aromatichydrocarbon solvents such as benzene toluene or the like; aliphatichydrocarbon solvents such as hexane, heptane or the like; ether solventssuch as diethyl ether, tetrahydrofuran, 1,4-dioxane or the like; amidesolvents such as hexamethyl phosphoric amide, dimethylformamide or thelike; polar solvents such as acetonitrile, propionitrile, acetone,diethyl ketone, methyl isobutyl ketone, cyclohexanone or the like; andhalogenated solvents such as dichloromethane, dichloroethane,chlorobenzene, dichlorobenzene or the like; and protonic solvents suchas methanol, ethanol, isopropanol, butanol or the like. These solventsmay be used alone or as a mixture of at least two of them. The amountthereof is usually 1 to 200 parts by weight, preferably 3 to 50 parts byweight, per part by weight of the phosphine compound of formula (24C).

The reaction temperature is usually in the range of from −100° C. ormore to the boiling point or less of the solvent, more preferably in therange of −80° C. to 100° C.

After the reaction, the phosphine compound of formula (24B) can beobtained from the reaction mixture by a conventional method, such asremoving the solvent by evaporation. The reaction product can bepurified by silica gel chromatography, if necessary.

Examples of the compound of formula (24C) include, for example, thefollowing compounds:

Examples of the compound of formula (1) wherein G² in is G²⁵, whichcorresponds to the compound of formula (25A) include, for example, thefollowing compounds:

Examples of the compound of formula (1) wherein G² represents G²⁵, whichcorresponds to the compound of formula (25B) include, for example, thefollowing compounds:

The phosphine compound of formula (25B) can be produced by reacting thephosphine halide compound of formula (25C) with the metal aryl compoundof formula (25D). The molar ratio between the phosphine halide compoundof formula (25C) and the metal aryl compound of formula (25D) is notparticularly restricted, and the ratio is preferably in the range of1:0.1 to 1:10, more preferably 1:0.5 to 1:5.

Specific examples of the halogen atom represented by X² in the compoundof formula (25C) or (25D) include fluorine, chlorine, bromine and iodineatoms. Chlorine atom is preferred.

Specific examples of the alkali metal represented by D in the metal arylcompound include lithium, sodium and potassium atoms, and lithium atomis preferable among them. Specific examples of the alkaline earth metalrepresented by J include magnesium and calcium atoms, and magnesium atomis preferable.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include, for example, aprotic solventsincluding aromatic hydrocarbon solvents such as benzene and toluene;aliphatic hydrocarbon solvents such as hexane, heptane or the like;ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane orthe like; polar solvents such as acetonitrile, acetone, diethyl ketone,methyl isobutyl ketone, cyclohexanone, ethyl acetate or the like; andhalogenated solvents such as dichloromethane, dichloroethane,chlorobenzene, dichlorobenzene or the like; and protonic solvents suchas methanol, ethanol, isopropanol, butanol or the like. These solventsmay be used alone or as a mixture of at least two of them. The amountthereof is usually 1 to 200 parts by weight, preferably 3 to 50 parts byweight, per part by weight of the metal aryl compound of formula (6).

The reaction temperature is usually in the range of from −100° C. ormore to the boiling point or less of the solvent, more preferably in therange of −80° C. to 100° C.

The phosphine compound of formula (3) can be obtained from the reactionmixture by a conventional method such as removing the solvent byevaporation. The reaction product can be purified by recrystallizationand silica gel chromatography, if necessary.

The phosphine compound of formula (25B) can be produced by reactingphosphine dihalide of formula (25E) with the metal aryl compound offormula (25F).

The molar ratio between phosphine dihalide of formula (25E) and themetal aryl compound of formula (25F) is not particularly limited, and itpreferably in the range of 1:0.1 to 1:10, more preferably in the rangeof 1:1.5 to 1:5.

Specific examples of the halogen atom represented by X² in the compoundof formula (25E) or (25F) include fluorine, chlorine, bromine and iodineatoms, and chlorine atom is preferable.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include aprotic solvents includingaromatic hydrocarbon solvents such as benzene, toluene or the like;aliphatic hydrocarbon solvents such as hexane, heptane or the like;ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane orthe like; polar solvents such as acetonitrile, propionitrile, acetone,diethylketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate orthe like; and halogenated solvents such as dichloromethane,dichloroethane, chlorobenzene, dichlorobenzene or the like; and protonicsolvents such as methanol, ethanol, isopropyl alcohol, butanol or thelike. These solvents may be used alone or as a mixture of at least twoof them. The amount thereof is usually 1 to 200 parts by weight,preferably 3 to 50 parts by weight, per part by weight of the metal arylcompound of formula (25F).

The reaction temperature is usually in the range of from −100° C. ormore to the boiling point or less of the solvent, more preferably in therange of −80° C. to 100° C.

The phosphine compound of formula (25E) can be obtained from thereaction mixture by a conventional method such as removing the solventby evaporation. The reaction product can be purified by silica gelchromatography, if necessary.

The metal aryl compound of formula (25D) can be produced by reacting afluorine-containing compound of formula (25G):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁷ and R¹⁸, and X and m are as described above,with, for example, a lithiating agent or magnesium metal.

The molar ratio between the metal aryl compound of formula (25G) and thelithiating agent or magnesium metal is not particularly restricted, andit is preferably in the range of 1:0.1 to 1:5, more preferably in therange of 1:0.5 to 1:2.5.

Examples of the lithiating agent include methyl lithium, n-butyllithium, s-butyl lithium, t-butyl lithium, phenyl lithium and the like,and n-butyl lithium is preferable.

Specific examples of the halogen represented by X in thefluorine-containing compound of formula (25G) include fluorine,chlorine, bromine and iodine atoms, preferably chlorine atom.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include aromatic hydrocarbon solventssuch as benzene, toluene or the like; aliphatic hydrocarbon solventssuch as hexane, heptane or the like; and ether solvents such as diethylether, tetrahydrofuran or the like. These solvents may be used alone oras a mixture of at least two of them. The amount thereof is usually 1 to200 parts by weight, preferably 3 to 50 parts by weight, per part byweight of the fluorine-containing compound of formula (25G).

The reaction can be performed by adding, for example, the lithiatingagent or magnesium metal to the fluorine-containing compound of formula(25G). The reaction temperature is usually in the range of from −100° C.or more to the boiling point or less of the solvent, and preferably inthe range of −100° C. to 100° C.

The phosphine dihalide of formula (25E) can be produced by reacting thephosphine dihalide represented by P(X²)₃, wherein X² represents ahalogen atom, with the metal aryl compound of formula (25D). The molarratio between the phosphine halide and the metal aryl compound offormula (25D) is not particularly restricted, and the ratio ispreferably in the range of 1:0.1 to 1:5, more preferably in the range of1:0.5 to 1:2.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include aromatic hydrocarbon solventssuch as benzene, toluene or the like; aliphatic hydrocarbon solventssuch as hexane, heptane or the like; and ether solvents such as diethylether, tetrahydrofuran or the like. These solvents may be used alone oras a mixture at least two of them. The amount thereof is usually 1 to200 parts by weight, preferably 3 to 50 parts by weight, per part byweight of the metal aryl compound of formula (25D).

The reaction can be performed by adding, for example, phosphinetrihalide to the metal aryl compound of formula (25D). The reactiontemperature is usually in the range of from −100° C. or more to theboiling point or less of the solvent, more preferably in the range of−80° C. to 100° C.

Phosphine dihalide of formula (25E) is obtained, for example, byremoving insolubles by filtration followed by removing the solvent byevaporation. The product can be purified by, for example, distillation,if necessary.

Examples of the metal aryl compound of formula (25F) include, forexample, the following compounds:

Examples of the phosphine dihalide of formula (25E) include, forexample, the following compounds:

2-fluorophenyl dichlorophosphine, 2,6-difluorophenyl dichlorophosphine,2,4,6-trifluorophenyl dichlorophosphine, pentafluorophenyldichlorophosphine, 2-fluoro-6-methyl dichlorophosphine,2-fluoro-6-tert-butylphenyl dichlorophosphine,2-fluoro-4,6-dimethylphenyl dichlorophosphine,2-fluoro-4,6-di(tert-butyl)phenyl dichlorophosphine,2-fluoro-4-methyl-6-tert-butylphenyl dichlorophosphine,2-fluoro-5-phenylphenyl dichlorophosphine, 2-fluoro-4-phenylphenyldichlorophosphine, 2-fluoro-6-phenylphenyl dichlorophosphine,2-fluoro-5-benzylphenyl dichlorophosphine, 2-fluoro-4-benzylphenyldichlorophosphine, 2-fluoro-6-benzylphenyl dichlorophosphine,2-fluoro-5-phenoxyphenyl dichlorophosphine, 2-fluoro-4-phenoxyphenyldichlorophosphine, 2-fluoro-6-phenoxyphenyl dichlorophosphine,2-fluoro-5-methoxyphenyl dichlorophosphine, 2-fluoro-4-methoxyphenyldichlorophosphine, 2-fluoro-6-methoxyphenyl dichlorophosphine,2-fluoro-5-trimethylsilylphenyl dichlorophosphine,2-fluoro-4-trimethylsilylphenyl dichlorophosphine,2-fluoro-6-trimethylsilylphenyl dichlorophosphine,2-fluoro-5-dimethylaminophenyl dichlorophosphine,2-fluoro-4-dimethylaminophenyl dichlorophosphine,2-fluoro-6-dimethylaminophenyl dichlorophosphine,

2-fluorophenyl dibromophosphine, 2,6-difluorophenyl dibromophosphine,2,4,6-trifluorophenyl dibromophosphine, pentafluorophenyldibromophosphine, 2-fluoro-6-methylphenyl dibromophosphine,2-fluoro-6-tert-butylphenyl dibromophosphine,2-fluoro-4,6-di(tert-butyl)phenyl dibromophosphine,2-fluoro-4-methyl-6-tert-butylphenyl dibromophosphine,2-fluoro-5-phenylphenyl dibromophosphine, 2-fluoro-4-phenylphenyldibromophosphine, 2-fluoro-6-phenylphenyl dibromophosphine,2-fluoro-5-benzylphenyl dibromophosphine, 2-fluoro-4-benzylphenyldibromophosphine, 2-fluoro-6-benzylphenyl dibromophosphine,2-fluoro-5-phenoxyphenyl dibromophosphine, 2-fluoro-4-phenoxyphenyldibromophosphine, 2-fluoro-6-phenoxyphenyl dibromophosphine,2-fluoro-5-methoxyphenyl dibromophosphine, 2-fluoro-4-methoxyphenyldibromophosphine, 2-fluoro-6-methoxyphenyl dibromophosphine,2-fluoro-5-trimethylsilylphenyl dibromophosphine,2-fluoro-4-trimethylsilylphenyl dibromophosphine,2-fluoro-6-trimethylsilylphenyl dibromophosphine,2-fluoro-5-dimethylaminophenyl dibromophosphine,2-fluoro-4-dimethylaminophenyl dibromophosphine,2-fluoro-6-dimethylaminophenyl dibromophosphine,

2-trifluoromethylphenyl dibromophosphine, 2,6-bistrifluoromethylphenyldichlorophosphine, 2,4,6-tristrifluoromethylphenyl dichlorophosphine,2-trifluoromethyl-6-methylphenyl dichlorophosphine,2-trifluoromethyl-6-tert-butylphenyl dichlorophosphine,2-trifluoromethyl-4,6-dimethylphenyl dichlorophosphine,2-trifluoromethyl-4,6-di(tert-butyl)phenyl dichlorophosphine,2-trifluoromethyl-4-methyl-6-tert-butylphenyl dichlorophosphine,2-trifluoromethyl-5-phenylphenyl dichlorophosphine,2-trifluoromethyl-4-phenylphenyl dichlorophosphine,2-trifluoromethyl-6-phenylphenyl dichlorophosphine,2-trifluoromethyl-5-benzylphenyl dichlorophosphine,2-trifluoromethyl-4-benzylphenyl dichlorophosphine,2-trifluoromethyl-6-benzylphenyl dichlorophosphine,2-trifluoromethyl-5-phenoxyphenyl dichlorophosphine2-trifluoromethyl-4-phenoxyphenyl dichlorophosphine,2-trifluoromethyl-6-phenoxyphenyl dichlorophosphine,2-trifluoromethyl-5-methoxyphenyl dichlorophosphine,2-trifluoromethyl-4-methoxyphenyl dichlorophosphine,2-trifluoromethyl-6-methoxyphenyl dichlorophosphine,2-trifluoromethyl-5-trimethylsilylphenyl dichlorophosphine,2-trifluoromethyl-4-trimethylsilylphenyl dichlorophosphine,2-trifluoromethyl-6-trimethylsilylphenyl dichlorophosphine,2-trifluoromethyl-5-dimethylaminophenyl dichlorophosphine,2-trifluoromethyl-4-dimethylaminophenyl dichlorophosphine,2-trifluoromethyl-6-dimethylaminophenyl dichlorophosphine,

2-trifluoromethylphenyl dibromophosphine, 2,6-bistrifluoromethylphenyldibromophosphine, 2,4,6-tristrifluoromethylphenyl dibromophosphine,2-trifluoromethyl-6-methylphenyl dibromophosphine,2-trifluoromethyl-6-tert-butylphenyl dibromophosphine,2-trifluoromethyl-4,6-dimethylphenyl dibromosphine,2-trifluoromethyl-4,6-di(tert-butyl)phenyl dibromophosphine,2-trifluoromethyl-4-methyl-6-tert-butylphenyl dibromophosphine,2-trifluoromethyl-5-phenylphenyl dibromophosphine,2-trifluoromethyl-4-phenylphenyl dibromophosphine,2-trifluoromethyl-6-phenylphenyl dibromophosphine,2-trifluoromethyl-5-benzylphenyl dibromophosphine,2-trifluoromethyl-4-benzylphenyl dibromophosphine,2-trifluoromethyl-6-benzylphenyl dibromophosphine,2-trifluoromethyl-5-phenoxyphenyl dibromophosphine,2-trifluoromethyl-4-phenoxyphenyl dibromophosphine,2-trifluoromethyl-6-phenoxyphenyl dibromophosphine,2-trifluoromethyl-5-methoxyphenyl dibromophosphine,2-trifluoromethyl-4-methoxyphenyl dibromophosphine,2-trifluoromethyl-6-methoxyphenyl dibromophosphine,2-trifluoromethyl-5-trimethylsilylphenyl dibromophosphine,2-trifluoromethyl-4-trimethylsilylphenyl dibromophosphine,2-trifluoromethyl-6-trimethylsilylphenyl dibromophosphine,2-trifluoromethyl-5-dimethylaminophenyl dibromophosphine,2-trifluoromethyl-4-dimethylaminophenyl dibromophosphine, and2-trifluoromethyl-6-dimethylaminophenyl dibromophosphine.

Examples of the fluorine-containing compound of formula (25G) include,for example, the following compounds:

2-fluorobromobenzene, 2,6-difluorobromobenzene,2,4-difluorobromobenzene, 2,3-difluorobromobenzene,2,4,6-trifluorobromobenzene, 2,4,5-trifluorobromobenzene,2,3,5,6-pentafluorobromobenzene, tetrafluorobromobenzene,2-fluoro-5-methylbromobenzene, 2-fluoro-4-methylbromobenzene,2-fluoro-4,6-dimethylbromobenzene,2-fluoro-4,6-di-tert-butylbromobenzene,2-fluoro-4-methyl-6-tert-butylbromobenzene,2-fluoro-6-methyl-4-tert-butylbromobenzene,2-fluoro-5-phenylbromobenzene, 2-fluoro-4-phenylbromobenzene,2-fluoro-4,6-diphenylbromobenzene, 2-fluoro-5-benzylbromobenzene,2-fluoro-4-benzylbromobenzene, 2-fluoro-4,6-dibenzylbromobenzene,2-fluoro-5-methoxybromobenzene, 2-fluoro-4-methoxybromobenzene,2-fluoro-4,6-dimethoxybromobenzene, 2-fluoro-5-aminobromobenzene,2-fluoro-4-aminobromobenzene, 2-fluoro-4,6-diaminobromobenzene,2-fluoro-5-(dimethylamono)bromobenzene,2-fluoro-4-(dimethylamono)bromobenzene,2-fluoro-4,6-bis(dimethylamino)bromobenzene,2-fluoro-5-(trimethylsilyl)bromobenzene,2-fluoro-4-(trimethylsilyl)bromobenzene,2-fluoro-4,6-bis(trimethylsilyl)bromobenzene,

2-trifluoromethylbromobenzene, 2,6-bis(trifluoromethyl)bromobenzene,2,4-bis(trifluoromethyl)bromobenzene,2,3-bis(trifluoromethyl)bromobenzene,2,4,6-tris(trifluoromethyl)bromobenzene,2,4,5-tris(trifluoromethyl)bromobenzene,2-trifluoromethyl-5-methylbromobenzene,2-trifluoromethyl-4-methylbromobenzene,2-trifluoromethyl-4,6-dimethylbromobenzene,2-trifluoromethyl-4,6-di-tert-butylbromobenzene,2-trifluoromethyl-4-methyl-6-tert-butylbromobenzene,2-trifluoromethyl-6-methyl-4-tert-butylbromobenzene,2-trifluoromethyl-5-phenylbromobenzene,2-trifluoromethyl-4-phenylbromobenzene,2-trifluoromethyl-4,6-diphenylbromobenzene,2-trifluoromethyl-5-benzylbromobenzene,2-trifluoromethyl-4-benzylbromobenzene,2-trifluoromethyl-4,6-dibenzylbromobenzene,2-trifluoromethyl-5-methoxybromobenzene,2-trifluoromethyl-4-methoxybromobenzene,2-trifluoromethyl-4,6-dimethoxybromobenzene,2-trifluoromethyl-5-aminobromobenzene,2-trifluoromethyl-4-aminobromobenzene,2-trifluoromethyl-4,6-diaminobromobenzene,2-trifluoromethyl-5-(dimethylamino)bromobenzene,2-trifluoromethyl-4-(dimethylamino)bromobenzene,2-trifluoromethyl-4,6-bis(dimethylamino)bromobenzene,2-trifluoromethyl-5-(trimethylsilyl)bromobenzene,2-trifluoromethyl-4-(trimethylsilyl)bromobenzene,2-trifluoromethyl-4,6-bis(trimethylsilyl)bromobenzene,

2-fluorochlorobenzene, 2,6-difluorochlorobenzene,2,4-difluorochlorobenzene, 2,3-difluorochlorobenzene,2,4,6-trifluorochlorobenzene, 2,4,5-trifluorochlorobenzene,2,3,5,6-pentafluorochlorobenzene, tetrafluorochlorobenzene,2-fluoro-5-methylchlorobenzene, 2-fluoro-4-methylchlorobenzene,2-fluoro-4,6-dimethylchlorobenzene,2-fluoro-4,6-di-tert-butylchlorobenzene,2-fluoro-4-methyl-6-tert-butylchlorobenzene,2-fluoro-6-methyl-4-tert-butylchlorobenzene,2-fluoro-5-phenylchlorobenzene, 2-fluoro-4-phenylchlorobenzene,2-fluoro-4,6-diphenylchlorobenzene, 2-fluoro-5-benzylchlorobenzene,2-fluoro-4-benzylchlorobenzene, 2-fluoro-4,6-dibenzylchlorobenzene,2-fluoro-5-methoxychlorobenzene, 2-fluoro-4-methoxychlorobenzene,2-fluoro-4,6-dimethoxychlorobenzene, 2-fluoro-5-aminochlorobenzene,2-fluoro-4-aminochlorobenzene, 2-fluoro-4,6-diaminochlorobenzene,2-fluoro-5-(dimethylamino)chlorobenzene,2-fluoro-4-(dimethylamino)chlorobenzene,2-fluoro-4,6-bis(dimethylamino)chlorobenzene,2-fluoro-5-(trimethylsilyl)chlorobenzene,2-fluoro-4-(trimethylsilyl)chlorobenzene,2-fluoro-4,6-bis(trimethylsilyl)chlorobenzene,

2-trifluoromethylchlorobenzene, 2,6-bis(trifluoromethyl)chlorobenzene,2,4-bis(trifluoromethyl)chlorobenzene,2,3-bis(trifluoromethyl)chlorobenzene,2,4,6-tris(trifluoromethyl)chlorobenzene,2,4,5-tris(trifluoromethyl)chlorobenzene,2-trifluoromethyl-5-methylchlorobenzene,2-trifluoromethyl-4-methylchlorobenzene,2-trifluoromethyl-4,6-dimethylchlorobenzene,2-trifluoromethyl-4,6-di-tert-butylchlorobenzene,2-trifluoromethyl-4-methyl-6-tert-butylchlorobenzene,2-trifluoromethyl-6-methyl-4-tert-butylchlorobenzene,2-trifluoromethyl-5-phenylchlorobenzene,2-trifluoromethyl-4-phenylchlorobenzene,2-trifluoromethyl-4,6-diphenylchlorobenzene,2-trifluoromethyl-5-benzylchlorobenzene,2-trifluoromethyl-4-benzylchlorobenzene,2-trifluoromethyl-4,6-dibenzylchlorobenzene,2-trifluoromethyl-5-methoxychlorobenzene,2-trifluoromethyl-4-methoxychlorobenzene,2-trifluoromethyl-4,6-dimethoxychlorobenzene,2-trifluoromethyl-5-aminochlorobenzene,2-trifluoromethyl-4-aminochlorobenzene,2-trifluoromethyl-4,6-diaminochlorobenzene,2-trifluoromethyl-5-(dimethylamino)chlorobenzene,2-trifluoromethyl-4-(diaminomethyl)chlorobenzene,2-trifluoromethyl-4,6-bis(dimethylamino)chlorobenzene,2-trifluoromethyl-5-(trimethylsilyl)chlorobenzene,2-trifluoromethyl-4-(trimethylsilyl)chlorobenzene, and2-trifluoromethyl-4,6-bis(trimethylsilyl)chlorobenzene.

Examples of the compound of formula (1) wherein G² is G²⁶, whichcorresponds to the compound of formula (26A) include, the followingcompounds:

Examples of the compound of formula (1) wherein G² in formula 1 is G²⁶,which corresponds to the compound of formula (26B) include, for example,the following compounds:

The phosphine compound of formula (26B) can be produced by reactingphosphine dihalide of formula (26C) with the metal aryl compound offormula (26D).

The molar ratio between phosphine dihalide of formula (26C) and themetal aryl compound of formula (26D) is not particularly restricted, andit is preferably in the range of 1:0.5 to 1:5, more preferably 1:1 to1:2.5.

Preferable examples of the halogen atom represented by X² in formula(26C) or (26D) include chlorine, bromine and iodine atoms, and thechlorine atom is preferable.

Specific examples of the alkali metal and alkaline earth metalrepresented by D in formula (26D) include lithium, sodium, potassium,magnesium and calcium atoms, and the lithium and magnesium atoms arepreferable.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include aromatic hydrocarbon solventssuch as benzene, toluene or the like; aliphatic hydrocarbon solventssuch as hexane, heptane or the like; and ether solvents such as diethylether, tetrahydrofuran or the like. These solvents may be used alone oras a mixture of at least two of them. The amount thereof is usually 1 to200 parts by weight, preferably 3 to 50 parts by weight, per part byweight of the metal aryl compound of formula (25D).

The reaction can be performed by adding, for example, phosphine dihalideof formula (26C) to the metal aryl compound of formula (26D). Thereaction temperature is usually in the range of from −100° C. or more tothe boiling point or less of the solvent, more preferably in the rangeof −80° C. to 100° C.

The phosphine compound of formula (26B) is obtained, for example, byremoving insolubles by filtration followed by removing the solvent byevaporation. The product can be purified by silica gel columnchromatography, if necessary.

The phosphine compound of formula (26B) can be produced by reactingphosphine halide of formula (26E) with the aryl compound of formula(26F).

The molar ratio between phosphine halide of formula (26E) and the arylcompound of formula (26F) in the reaction is not particularlyrestricted, and the ratio is preferably in the range of 1:0.1 to 1:5,more preferably 1:0.5 to 1:2.

Specific examples of the halogen atom represented by X² in formula (26E)or (26F) include fluorine, chlorine, bromine and iodine atoms, and thechlorine atom is preferable.

Specific examples of the alkali metal and alkaline earth metalrepresented by D in formula (26F) include lithium, sodium, potassium,magnesium and calcium atoms, and lithium and magnesium atoms arepreferable.

The reaction above is usually performed in a solvent inert to thereaction. Examples of the solvent include aromatic hydrocarbon solventssuch as benzene, toluene or the like; aliphatic hydrocarbon solventssuch as hexane, heptane or the like; and ether solvents such as diethylether, tetrahydrofuran or the like. These solvents may be used alone oras a mixture of at least two of them. The amount thereof is usually 1 to200 parts by weight, preferably 3 to 50 parts by weight, per part byweight of the metal aryl compound of formula (8).

The reaction can be performed by adding, for example, phosphine halideof formula 26E to the aryl compound of formula (26F). The reactiontemperature is usually in the range of from −100° C. or more to theboiling point or less of the solvent, more preferably in the range of−80° C. to 100° C.

The phosphine compound of formula (26B) is obtained, for example, byremoving insolubles by filtration followed by removing the solvent byevaporation. The product may be purified by silica gel columnchromatography, if necessary.

Specific examples of phosphine dihalide of formula (26C) include, forexample, the following compounds:

The compounds of formulae above also include those in which the chlorineatom is replaced by bromine or iodine atoms.

Specific examples of the metal aryl compound of formula (26D) include,for example, the following compounds:

Specific examples of phosphine halide of formula (26E) include, forexample, the following compounds:

Specific examples of the aryl compound of formula (26F) include, forexample, the following compounds:

Transition metal complexes of the invention obtained by reacting theligand of formula 2 with the transition metal compound of formula 4 willbe described below.

Examples of the group 4 element represented by M in formula 4 includetitanium, zirconium and hafnium. Titanium and zirconium are preferable.

Examples of the halogen atom represented by X¹ in formula 4 includefluorine, chlorine, bromine and iodine atoms. Chlorine atom ispreferable.

Specific examples of the alkyl group having 1 to 10 carbon atom(s) thatmay be substituted, represented by X¹, include methyl group, ethylgroup, n-propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexylgroup, n-octyl group and n-decyl group. Specific examples of the groupssubstituted with a halogen atom, alkoxy group, aryloxy group, ahydrocarbon-substituted amino group, or a silyl group substituted with ahydrocarbon include, for example, fluoromethyl group, difluoromethylgroup, trifluoromethyl group, fluoroethyl group, difluoroethyl group,trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group,perfluoropropyl group, perfluorobutyl group, perfluoropentyl group,perfluorohexyl group, perfluorooctyl perfluorodecyl trichloromethylgroup, methoxymethyl group, phenoxymethyl group, dimethylaminomethylgroup and trimethylsilyl group. Of the alkyl group having 1 to 10 carbonatom(s) that may be substituted, methyl, ethyl, isopropyl, tert-butyland amyl groups are preferable, and methyl group is more preferable.

Examples of the aralkyl group having 7 to 20 carbon atoms that may besubstituted, represented by X¹, include benzyl, naphthylmethyl,anthracenylmethyl and diphenylmethyl groups, including those substitutedwith a halogen atom, alkyl group, alkoxy group, aryloxy group, ahydrocarbon-substituted amino group, or with a silyl group substitutedwith hydrocarbon. Specific examples thereof include(2-methylphenyl)methyl group, (3-methylphenyl)methyl group,(4-methylphenyl)methyl group, (2,3-dimethylphenyl)methyl group,(2,4-dimethylphenyl)methyl group, (2,5-dimethylphenyl)methyl group,(2,6-dimethylphenyl)methyl group, (3,4-dimethylphenyl)methyl group,(2,3,4-trimethylphenyl)methyl group, (2,3,5-trimethylphenyl)methylgroup, (2,3,6-trimethylphenyl)methyl group,(3,4,5-trimethylphenyl)methyl group, (2,4,6-trimethylphenyl)methylgroup, (2,3,4,5-tetramethylphenyl)methyl group,(2,3,4,6-tetramethylphenyl)methyl group,(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methylgroup, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,(sec-butylphenyl)methyl (tert-butylphenyl)methyl group,(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,(n-hexylphenyl)methyl (n-octylphenyl)methyl group, (n-decylphenyl)methylgroup, (n-dodecylphenyl)methyl group, (fluorophenyl)methyl(difluorophenyl)methyl group, (pentafluorophenyl)methyl group,(chlorophenyl)methyl group, (methoxyphenyl)methyl group,(phenoxyphenol)methyl group, (dimethylaminophenyl)methyl group and(trimethylsilylphenyl)methyl group. The aralkyl group having 7 to 20carbon atoms that may be substituted is preferably a benzyl group.

Examples of the aryl group having 6 to 20 carbon atoms that may besubstituted, represented by X¹, include phenyl, naphthyl and anthracenylgroups.

Further examples of the aryl group include those substituted a halogenatom, alkyl, alkoxy, aryloxy, a hydrocarbon-substituted amino group, orwith silyl group substituted with a hydrocarbon. Specific examplesthereof include 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylylgroup, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylylgroup, 3,5-xylyl group, 2,3,4-trimethylphenyl group,2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group,2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group,2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group,2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenylgroup, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group,sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group,neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group,n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group,2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group,3,5-difluorophenyl group, pentafluorophenyl group, 4-chlorophenyl group,2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group,4-phenoxyphenyl group, 4-dimethylaminophenol group and4-trimethylsilylphenyl group. Aryl group that may be substituted ispreferably a phenyl group.

Specific examples of the alkoxy group having 1 to 10 carbon atom(s) thatmay be substituted, represented by X¹, include methoxy group, ethoxygroup, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxygroup, tert-butoxy group, n-pentyloxy group, neopentyloxy group,n-hexyloxy group, n-octyloxy group, n-nonyloxy group and n-decyloxygroup. These groups may be further substituted, and examples thereofinclude those substituted with a halogen atom, an alkoxy, aryloxy,hydrocarbon-substituted amino, or with a silyl group substituted with ahydrocarbon.

Specific examples of the substituted alkoxy group include fluoromethoxygroup, fluoroethoxy group, difluoromethoxy group, trifluoromethoxygroup, fluoroethoxy group, difluoroethoxy group, trifluoroethoxy group,tetrafluoroethoxy group, pentafluoroethoxy group, perfluoropropoxygroup, perfluorobutyloxy group, perfluoropentyloxy group,perfluorohexyloxy group, perfluorooctyloxy group, perfluorodecyloxygroup, trichloromethyloxy group, methoxymethoxy group, phenoxymethoxygroup, dimethylaminomethoxy group, trimethylsilylmethoxy group and thelike. The alkoxy group having 1 to 10 carbon atom(s) that may besubstituted is preferably a methoxy group.

Examples of the aralkyloxy group having 7 to 20 carbon atoms,represented by X¹, include benzyloxy group, naphthylmethoxy group,anthracenylmethoxy group and diphenylmethoxy group. These may be furthersubstituted, and examples thereof include those substituted with ahalogen atom, an alkyl group, an alkoxy group, an aryloxy group, ahydrocarbon-substituted amino group, or with a silyl group substitutedwith a hydrocarbon. Specific examples thereof include(2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group,(4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group,(2,4-dimethylphenyl)methoxy group, (2,5-dimethylphenyl)methoxy group,(2,6-dimethylphenyl)methoxy group, (3,4-dimethylphenyl)methoxy group,(2,3,4-trimethylphenyl)methoxy group, (2,3,5-trimethylphenyl)methoxygroup, (2,3,6-trimethylphenyl)methoxy group,(3,4,5-trimethylphenyl)methoxy group, (2,4,6-trimethylphenyl)methoxygroup, (2,3,4,5-tetramethylphenyl)methoxy group,(2,3,4,6-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, (ethylphenyl)methoxy group, (n-propylphenyl)methoxy group,(isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group,(sec-butylphenyl)methoxy group, (tert-butylphenyl)methoxy group,(n-pentylphenyl)methoxy group, (neopentylphenyl)methoxy group,(n-hexylphenyl)methoxy group, (n-octylphenyl)methoxy group,(n-decylphenyl)methoxy group, (n-dodecylphenyl)methoxy group,(fluorophenyl)methyl group, (difluorophenyl)methyl group,(pentafluorophenyl)methyl group, (chlorophenyl)methyl group,(methoxyphenyl)methyl group, (phenoxyphenyl)methyl(dimethoxyaminophenyl)methyl group and (trimethoxysilylphenyl)methylgroup. The aralkyloxy group having 7 to 20 carbon atoms that may besubstituted is preferably a benzyloxy group.

Examples of the aryloxy group having 6 to 20 carbon atoms that may besubstituted in X¹ include phenoxy, naphthoxy and anthracenoxy groups.These groups may be further substituted, and examples thereof includethose substituted with a halogen atom, an alkyl group, an alkoxy group,an aryloxy group, a hydrocarbon-substituted amino group, or with a silylgroup substituted with a hydrocarbon. Specific examples thereof include2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group,2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group,2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group,2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group,2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group,2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group,2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxygroup, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxygroup, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxygroup, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxygroup, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxygroup; 3,5-difluorophenoxy group, pentafluorophenoxy group,4-chlorophenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group,4-methoxyphenoxy group, 4-phenoxyphenoxy group, 4-dimethylaminophenoxygroup and 4-trimethylsilylphenoxy group. The aryloxy group having 7 to20 carbon atoms that may be substituted is preferably a phenoxy group.

In the amino group disubstituted with substituted or unsubstitutedhydrocarbon group having 1 to 20 carbon atom(s), represented by X¹,examples of the hydrocarbon include alkyl groups having 1 to 10 carbonatom(s) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl n-pentyl, neopentyl, amyl, n-hexyl, cyclohexyl, n-octyl, orn-decyl group; and aryl groups having 6 to 20 carbon atoms such asphenyl, tolyl, xylyl, naphthyl or anthracenyl group. Examples of theamino group substituted with the hydrocarbon groups having 1 to 20carbon atom(s) include dimethylamino group, diethylamino group,di-n-propylamino group, diisopropylamino group, di-n-butylamino group,di-sec-butylamino group, di-tert-butylamino group, di-isobutylaminogroup, tert-butylisopropylamino group, di-n-hexylamino group,di-n-octylamino group, di-n-decylamino group, diphenylamine group andthe like. The dimethylamino and diethylamino groups are preferable.

The neutral ligand represented by L or L¹ denotes a molecule having aneutral functional group(s) such as ether, sulfide, amine, phosphine orolefin, and it may possess coordinating functional groups at a pluralityof sites in the molecule.

Examples of the neutral ligand include dimethyl ether, diethyl ether,methyl tert-butyl ether, furan, tetrahydrofuran, dimethoxyethane,diethoxyethane, dimethyl sulfide, diethyl sulfide, methyl tert-butylsulfide, thiophene, tetrahydrothiophene, ethylenedithiol,dimethylsulfide, ethylenedithiol, diethylsulfide, trimethylamine,triethylamine, triphenylamine, tricyclohexylamine, pyridine,2,2′-bipyridine, tetramethylenediamine, tetraethylethylenediamine,triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine,bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane,bis(diphenylphosphino)propane, bis(diphenylphosphino)binaphthyl,ethylene, propylene, butene, butadiene, octene, octadiene, cyclohexene,cyclohexadiene, norbornene and norbornadiene.

Examples of the transition metal compound of formula (4) include, forexample, tetrabenzyl titanium, tetraneopentyl titanium, tetrachlorotitanium, tetraisopropoxy titanium, diisopropoxy titanium dichloride,tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium,bis(dimethylamino)titanium dichloride, bis(diethylamino)titaniumdichloride, tetrakis(trifluoroacetoxy)titanium,bis(trifluoroacetoxy)titanium dichloride, titaniumtrichloride-3tetrahydrofuran complex, titaniumtetrachloride-2tetrahydrofuran complex,

tetrabenzyl zirconium, tetraneopentyl zirconium, tetrachloro zirconium,tetraisopropoxy zirconium, diisopropoxy zirconium dichloride,tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium,bis(dimethylamino)zirconium dichloride, bis(diethylamino)zirconiumdichloride, tetrakis(trifluoroacetoxy) zirconium,bis(trifluoroacetoxy)zirconium dichloride,trichlorozirconium-3tetrahydrofuran complex,tetrachlorozirconium-2tetrahydrofuran complex,

tetrabenzyl hafnium, tetraneopentyl hafnium, tetrachlorohafnium,tetraisopropoxy hafnium, diisopropoxy hafnium dichloride,tetrakis(dimethylamino)hafnium, tetrakis(diethylamino)hafnium,bis(dimethylamino)hafnium dichloride, bis(diethylamino)hafniumdichloride, tetrakis(trifluoroacetoxy)hafnium,bis(trifluoroacetoxy)hafnium, trichlorohafnium 3-tetrahydrofurancomplex, tetrachlorohafnium 2-tetrahydrofuran complex and the like.

The transition metal complex is produced by reacting phosphine compoundof formula 2 with the transition metal compound of formula 4.

The ratio between the phosphine compound of formula (2) and thetransition metal compound of formula (4) is not particularly restricted,and it is preferably in the range of 1:0.1 to 1:10, more preferably inthe range of 1:0.5 to 1:2.

A base is used for the reaction, if necessary. Examples of the baseinclude organic alkali metal compounds including organic lithiumcompounds such as methyl lithium, ethyl lithium, n-butyl lithium,sec-butyl lithium, tert-butyl lithium, lithium trimethylsilylacetylide,lithium acetylide, trimethylsilylmethyl lithium, vinyl lithium, phenyllithium, allyl lithium or the like, and metal hydrides such as sodiumhydride, potassium hydride or the like. The amount thereof is usually inthe range of 0.5 to 5 mole per mol of the phosphine compound of formula(2).

The reaction is usually carried out in a solvent inert to the reaction.Examples of the solvent include aprotic solvents including aromatichydrocarbon solvents such as benzene, toluene or the like; aliphatichydrocarbon solvents such as hexane, heptane or the like; and ethersolvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane or thelike; amide solvents such as hexamethylphosphoric amide,dimethylformamide or the like; polar solvents such as acetonitrile,propionitrile, acetone, diethyl ketone, methyl isobutyl ketone,cyclohexanone or the like; and halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene or thelike. These solvents may be used alone or as a mixture of at least twoof them. The amount thereof is usually 1 to 200 parts by weight,preferably 3 to 50 parts by weight, per part by weight of the phosphinecompound of formula (2).

The reaction is usually carried out by adding the transition metalcompound of formula (4) to the phosphine compound of formula (2) in asolvent after adding a base, if necessary. The reaction temperature isusually in the range of −100° C. or more to the boiling point or less ofthe solvent, preferably in the range of −80 to 100° C.

The transition metal compound may be obtained from the reaction mixtureby a conventional method. For example, the precipitated substance isremoved by filtration, and a solid product is precipitated byconcentrating the filtrate.

The transition metal compound thus obtained is typically the transitionmetal compound of formula (3).

Examples of the compound having a partial structure corresponding toeach formula of G² in formula (3) include the following compounds.

Examples of the transition metal compound of formula (3) include, forexample, the following compounds:

The compounds in which the titanium atom is replaced by the zirconiumatom or hafnium atom can also be exemplified.

In the polymerization reaction, the transition metal complex thusproduced may be charged for use with compound A or compound B as anadditional component (s) in an optional order, or a products obtained bycontacting the components optionally selected from the components priorto the polymerization.

Organic aluminum compound known in the art may be used as compound A inthe invention. Preferably, the organic aluminum compound known in theart may be used as compound A, and any one of compounds A1 to A3, or amixture of at least two of them is preferable.

Examples of organic aluminum compound A1 represented by E1a-Al—Z3ainclude trialkylaluminum such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisobutylaluminum, trihexylaluminum or the like;dialkyl aluminum chloride such as dimethylaluminum chloride,diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminumchloride, dihexylaluminum chloride or the like; alkylaluminum dichloridesuch as methylaluminum dichloride, ethylaluminum dichloride,propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminumdichloride or the like; and dialkylaluminum hydride such asdimethylaluminum hydride, diethylaluminum hydride, dipropylaluminumhydride, diisobutylaluminum hydride, dihexylaluminum hydride or thelike. Trialkylaluminum is preferable, and triethylaluminum andtriisobutylaluminum are more preferable.

Specific examples of E2, E3 in cyclic aluminoxane (A2) having thestructure of formula [-A(E2)-O-]_(b) and in linear aluminozane ((A3)having the structure of formula E3[—Al(E3)-O-]_(c), respectively,include alkyl groups such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, n-pentyl, neopentyl or the like. b is an integer of2 or more, and c is an integer of 1 or more. Preferably, E2 or E3 is amethyl or isobutyl group, and b is 2 to 40 and c is 1 to 40,respectively. Specific examples of aluminoxane include methylaluminoxane (MAO), modified aluminoxane (MMAO) and butyl aluminoxane(BAO).

The aluminoxane can be produced by various methods. The method is notparticularly restricted, and the compound may be produced according tothe method known in the art. For example, the compound is by reacting asolution prepared by dissolving trialkylaluminum (for exampletrimethylaluminum) in a suitable solvent (such as benzene and aliphatichydrocarbon), with water. In another example, the compound is producedby contacting trialkylaluminum (for example trimethylaluminum) with ametal salt containing crystallization water (for example copper sulfatehydrate).

In the boron compound (B1) of formula BQ¹Q²Q³, Q¹ to Q³ are preferablyhalogen atoms, hydrocarbons having 1 to 20 carbon atom(s), orhalogenated hydrocarbons having 1 to 20 carbon atom(s).

Specific examples of B1 include tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane andphenylbis(pentafluorophenyl)borane. Preferred istris(pentafluorophenyl)borane.

In the boron compound (B2) of formula Z⁺(BQ¹Q²Q³Q⁴)⁻, examples of Q¹ toQ⁴ are the same as those exemplified for Q¹ to Q³ in the boron compound(B1).

In the specific example of the compound represented by Z⁺(BQ¹Q²Q³Q⁴)⁻,examples of inorganic cation Z⁺ include ferrocenium cation,alkyl-substituted ferrocenyl cation and silver cation, and examples oforganic cation Z⁺ include triphenylmethyl cation. Examples of(BQ¹Q²Q³Q⁴)⁻ include tetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenylbis(pentafluorophenyl)borate andtetrakis(3,5-bistrifluoromethylphenyl)borate.

Specific examples of the combination thereof include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate,triphenylmethyltetrakis(pentafluorophenyl)borate, andtriphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate.Triphenylmethyltetrakis(pentafluorophenyl)borate is preferable.

In the boron compound (B3) represented by (L-H)⁺(BQ¹Q²Q³Q⁴)⁻, Q¹ to Q⁴are the same as Q¹ to Q³ in B1 above.

As the specific examples of the compound represented by(L-H)⁺(BQ¹Q²Q³Q⁴)⁻, exemplified are those composed of Brønsted acid(L-H)⁺ such as trialkyl-substituted ammonium, N,N-dialkyl anilinium,dialkyl ammonium or triaryl phosphonium, and (BQ¹Q²Q³Q⁴)⁻ as exemplifiedabove.

Specific examples of the combination thereof include triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakisammonium tetrakis(3,5-bistrifluoromethylphenyl)borate,diisopropylammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate,triphenylphosphonium tetrakis(pentafluorophenyl)borate,tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.Preferred are tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and the like.

The ratio of each catalyst component is desirably in the range of 0.1 to10,000, more preferably in the range of 5 to 2000, for the molar ratioof compound A/transition metal complex (1), and more preferably in therange of 0.01 to 100, preferably in the range of 0.5 to 10, for themolar ratio of compound B/transition metal complex (1).

The concentration of each catalyst component used as a solution isdesirably in the range of 0.0001 to 5 mmol/L, preferably in the range of0.001 to 1 mmol/L, for transition metal complex (1); in the range of0.01 to 500 mmol/L, preferably in the range of 0.1 to 100 mmol/L interms of aluminum, for compound A; and in the range of 0.0001 to 5mmol/L, preferably in the range of 0.001 to 1 mmol/L, for compound B.

Any one of olefin and diolefin having 2 to 20 carbon atoms can be usedas the monomer for polymerization in the invention, and at least twomonomers can be used together. While the monomers are exemplified below,the invention is not restricted to these monomers. Specific examples ofolefin include ethylene, propylene, butene-1, pentene-1, hexene-1,heptene-1, octene-1, nonen-1, decen-1,5-methyl-2-pentene-1, vinylcyclohexene and the like. Examples of the diolefin compound includeconjugated diene and non-conjugated diene of the hydrocarbon compound,and specific examples of the non-conjugated diene compound include1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene,5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene,5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene,1,5-cyclooctadiene, 5,8-endomethylene hexahydronaphthalene and the like;and specific examples of the conjugated diene compound include1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene,1,3-cyclooctadiene, 1,3-cyclohexadiene and the like.

Specific examples of the monomer constituting the copolymer includeethylene and propylene, ethylene and butene-1, ethylene and hexene-1,and propylene and butene-1, as well as combinations further using5-ethylidene-2-norbornene thereto, the invention is not restricted tothese compounds.

Aromatic vinyl compounds can be used as the monomer in the invention.Specific examples of the aromatic vinyl compound include styrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene,o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene,p-chlorostyrene, α-methylstyrene, divinylstyrene and the like.

The polymerization method is not particularly restricted, and thepolymerization can be conducted by solvent polymerization using analiphatic hydrocarbon such as butane, pentane, hexane, heptane oroctane, aromatic hydrocarbon such as benzene or toluene, or halogenatedhydrocarbon such as methylene dichloride as the solvent, slurrypolymerization or gas phase polymerization using gaseous monomers.Continuous polymerization or batch-wise polymerization can be used.

The polymerization temperature can be set in the range of −50° C. to200° C. The temperature range of −20° C. to 100° C. is preferable. Thepolymerization reaction pressure is preferably in the range ofatmospheric pressure to 6 MPa (60 kg/cm²G). The polymerization reactiontime is appropriately selected depending on the kind of the desiredpolymer and reaction equipment, and it may be in the range of 1 minuteto 20 hours. A chain transfer agent such as hydrogen can be added in theinvention for controlling the molecular weight of the copolymer.

EXAMPLES

While the invention is described in more detail with reference toexamples, the invention is not restricted to these examples. Theproperties of the polymers in the examples were measured by thefollowing methods.

[Molecular Weight and Molecular Weight Distribution]

The molecular weight and molecular weight distribution were measured asfollows using Rapid GPC (trade name; manufactured by Symyx Co.).

Pump: (LC pump), manufactured by Gilson Co.

Model 1305 (trade name), pump head 25.SC

Column: PL gel Mixed-B (trade name; manufactured by Polymer Laboratories(PL) Co.), 10 μm,

7.5 mmφ×300 mm

Mobile phase: o-dichlorobenzene

Dissolving solvent: 1,2,4-trichlorobenzene

Flow rate: 2 ml/min

Column temperature: 160° C.

Calibration curve: polystyrene (PS, standard manufactured by PL Co.), 8samples

Standard molecular weight of PS; 5,000, 10,050, 28,500, 65,500, 185,400, 483,000, 1,013,000, 3,390,000

[Melting Point]

Melting point was measured under the following condition using SAMMS(Sensor Array Modular System, trade name, manufactured by Symyx Co.)

Measurement mode: melting temperature measurement by heat capacityspectroscopy

Atmospheric gas: vacuum (3.0×10⁻⁴ Torr or below)

Temperature program:

(start) room temperature

(rate of temperature increase) about 50° C./min

(hold) 200° C. (0 minute)

[Me Branching]

Me branching was measured under the following condition using IRspectrometer (EQINOX 55, trade name, manufactured by Bruker Co.)

Measurement mode: reflection-transmission method (a film is formed on amirror surface)

Blank: mirror surface (air)

Measuring condition:

(resolution) 2 cm⁻¹

(number of integration) 128 times

(wavelength) 400 to 4000 cm⁻¹

Example A1 Synthesis of Compound A1

A 1.56 M hexane solution (7.05 mL) of n-butyl lithium was added dropwiseinto a tetrahydrofuran solution (23.5 mL) of1-methoxymethoxy-2-tert-butyl-4-methylbenzene (2.08 g, 10.0 mmol) at−78° C., and the solution was warmed to room temperature with stirringfor 1 hour. The reaction solution was added into a tetrahydrofuransolution (23.5 ml) of phosphorous trichloride (0.69 g, 5.0 mmol) at −78°C., and the solution was warmed to room temperature with stirring for 5hours. Compound A1 was quantitatively obtained by removing the solventunder a reduced pressure after removing insoluble substances byfiltration.

¹H NMR (CD₂Cl₂) d1.38 (18H), 2.25 (6H), 3.60 (6H), 5.06-5.26 (4H),7.07-7.27 (4H)

³¹P NMR (CD₂Cl₂) 79.15

Example A2 Synthesis of Compound A2

A 1.56 M hexane solution (35.3 mL) of n-butyl lithium was added dropwiseinto a tetrahydrofuran solution (180.6 mL) of2-(o-bromophenyl)-1,3-dioxolane (11.15 g, 50.0 mol) at −78° C., and thesolution was warmed to room temperature with stirring for 2 hours. Thereaction mixture was cooled to −78° C., and a tetrahydrofuran solution(77.4 mL) of compound A1 (24.05 g, 50.0 mmol) was added therein followedby warming to room temperature with stirring for 10 hours. The reactionwas stopped by adding deionized water (200.0 mL) and toluene (200.0 mL),and the solvent was removed after washing the organic layer withsaturated aqueous sodium chloride solution (100 mL) to obtain a crudeproduct as a pale yellow oil. The crude product was purified by silicagel column chromatography (hexane/ethyl acetate=30/1 to 4/1) to obtaincompound A2 (9.52 g, yield 32.0%) as a white solid.

¹H NMR (CDCl₃) d1.37 (18H), 2.10 (6H), 3.45 (6H), 3.93-4.14 (4H),5.11-5.13 (4H), 5.20 (1H), 6.34 (2H), 6.44 (2H), 6.92-7.66 (4H)

Example A3 Synthesis of Compound A3

A 1.56 M hexane solution (21.2 mL) of n-butyl lithium was added dropwiseinto a diethylether solution (145.0 mL) of 2-(o-bromophenyl)-1,3-dioxane(6.87 g, 30.0 mmol) at −78° C., and the solution was warmed to roomtemperature with stirring for 2 hours. The mixed reaction solution wascooled to −78° C., and a diethylether solution (116.0 mL) of phosphoroustrichloride (8.24 g, 60.0 mmol) was added to the solution followed bywarming to room temperature with stirring for 10 hours. Compound A3 wasobtained by removing the solvent by evaporation in vacuum after removinginsoluble materials by filtration.

³¹P (CD₂Cl₂): δ 160.8

Example A4 Synthesis of Compound A2

A 1.56 M hexane solution (33.8 mL) of n-butyl lithium was added dropwiseinto a tetrahydrofuran solution (158 mL) of2-tert-butyl-1-methoxymethoxy-4-methylbenzene (10.0 g, 48.0 mmol) at−78° C., and the solution was warmed to room temperature with stirringfor 2 hours. The reaction mixture was cooled to −78° C., and atetrahydrofuran solution (67.5 mL) of compound A3 (6.03 g, 24.0 mmol)was added into the cooled solution, followed by warming to roomtemperature with stirring for 10 hours. Compound A2 was obtained byapplying the same post treatment to the resulting mixture as in ExampleA2.

Example A5 Synthesis of Compound A4

Into a solution of compound A2 (1.49 g, 2.50 mmol) in a mixed solvent oftetrahydrofuran/water=10/1 (46.3 mL), 98% sulfuric acid (1.32 g) wasadded at room temperature and the mixture was stirred for 3 hours. Thereaction was stopped by adding deionized water (70.0 mL) and toluene(50.0 mL). After washing the organic layer with saturated aqueous sodiumchloride solution (70 mL), the solvent was removed by evaporation toquantitatively obtain compound A4 as a pale yellow oil.

¹H NMR (CDCl₃) d1.40 (18H), 2.10 (6H), 3.50 (6H), 5.26 (4H), 6.27 (2H),6.97-7.98 (6H), 10.6 (1H)

Examples A6 Synthesis of Compound A5

Acetyl chloride (1.96 g, 25.0 mmol) was added to a solution of compoundA4 (2.75 g, 5.00 mmol) in a mixed solvent of ethyl acetate and methanol(1:1, 110.0 mL), and then the mixture was stirred for 15 hours at roomtemperature. A crude product was obtained as an yellow oil by removingthe solvent by evaporation in vacuum. The crude product was purified bysilica gel column chromatography to obtain 0.64 g of compound A5 (yield64.0%) as an yellow solid.

¹H NMR (CDCl₃) d1.34 (18H), 2.09 (6H), 6.33 (2H), 6.51 (2H), 7.07-7.87(6H), 10.1 (1H)

³¹P NMR (C₆D₆) d −52.8

Example A7 Synthesis of Compound A6

Tert-butylamine (0.91 g, 12.5 mmol) was added to a solution of compoundA4 (1.38 g, 2.50 mmol) in ethanol solution (62.4 mL), and the mixturewas heated to 40° C. and then stirred for 5 hours. Compound A6 wasquantitatively obtained by removing the solvent by evaporation.

¹H NMR (CDCl₃) d1.15 (9H), 1.40 (18H), 2.12 (6H), 3.50 (6H), 5.10-5.19(4H), 6.47 (2H), 6.90-7.95 (6H), 8.90 (1H)

¹³C NMR (CDCl₃) d21.1, 29.5, 30.8, 36.1, 57.2, 57.6, 99.5, 126.4, 142.8,154.5, 156.3

Example A8 Synthesis of Compound A7

Compound A7 can be obtained by adding acetyl chloride to a solution ofcompound A6 in a mixed solution of ethyl acetate and methanol (1:1) withstirring at room temperature, followed by removing the solvent under areduced pressure.

Example A9 Synthesis of Compound A8

Compound A8 was quantitatively obtained by the same manner as in ExampleA7, except that aminopiperidine was used in place of tert-butylamine.

¹H NMR (CDCl₃) d1.38-3.03 (10H), 1.40 (18H), 2.12 (6H), 3.48 (6H),5.08-5.18 (4H), 6.50 (2H), 6.89-7.92 (6H), 8.11 (1H)

Example A10 Synthesis of Compound A9

Compound A9 was quantitatively obtained by the same manner as in ExampleA7, except that aminopyrrole was used in place of tert-butylamine.

¹H NMR (CDCl₃) d1.40 (18H), 2.13 (6H), 3.51 (6H), 5.09-5.24 (4H), 6.48(2H), 7.01-8.12 (10H), 9.15 (1H)

Example A11 Synthesis of Compound A10

Aminopiperidine (0.03 g, 0.25 mmol) was added to a solution of compoundA5 (0.12 g, 0.25 mmol) in ethanol solution (44.0 mL) at 0° C. withstirring for 3 hours. Compound A10 was quantitatively obtained byremoving the solvent by evaporation.

Example A12 Synthesis of Compound A11

Compound A11 was quantitatively obtained by the same manner as inExample A11, except that aminopyrrole was used in place ofaminopiperidine.

¹H NMR (CDCl₃) d1.41 (18H), 2.16 (6H), 6.15 (2H), 6.67 (2H), 6.96-7.49(10H), 8.68 (1H)

Example A13 Synthesis of Compound A10

Compound A10 can be obtained by adding acetyl chloride to a solution ofcompound A8 in a mixed solvent of ethyl acetate and methanol (1:1) atroom temperature with stirring, and by removing the solvent byevaporation in vacuum.

Example A14 Synthesis of Compound A11

Compound A11 can be obtained by adding acetyl chloride to a solution ofcompound A9 in a mixed solvent of ethyl acetate and methanol (1:1) atroom temperature with stirring, and by removing the solvent byevaporation in vacuum.

Example A15 Synthesis of Complex A12

A toluene solution (2.31 mL) of titanium tetrachloride (0.08 g, 0.40mmol) was added dropwise into a toluene solution (2.31 mL) of compoundA6 (0.20 g, 0.33 mmol) at −78° C., and the solution was stirred for 10hours after warming to room temperature. Compound 12 (204.7 mg, yield97.5%) was obtained as a red solid by removing the solvent under areduced pressure after removing insoluble substances by filtration.

³¹P NMR (C₆D₆) d22.8

EI-MS 635 (M⁺¹)

Example A16 Synthesis of Complex A13

Complex A13 (289.3 mg) was obtained in 87.8% yield by the same manner asin Example A15, except that compound A8 was used in place of compoundA6.

¹H NMR (CD₂Cl₂) d1.27-2.00 (10H), 1.38 (18H), 2.34 (6H), 6.86 (2H), 7.06(2H), 7.48-8.15 (4H), 10.23 (1H)

³¹P NMR (C₆D₆) d7.16

EI-MS 626 (M-Cl)

Example A17 Synthesis of Complex A14

A 1.57 M solution of n-butyl lithium in hexane (0.64 mL) was addeddropwise into a tetrahydrofuran solution (4.45 mL) of compound A11 (0.26g, 0.50 mmol) at −78° C., and the solution was stirred for 1 hour afterwarming to room temperature. Then, a tetrahydrofuran solution (4.45 mL)of titanium tetrachloride/2-tetrahydrofuran complex (0.17 g, 0.50 mmol)was dripped into the mixed solution above at −78° C. in 2 hours. Afterwarming to room temperature, the reaction mixture was stirred for 10hours. After removal of the solvent by evaporation in vacuum, toluene(10.0 mL) was added to the residue. After removal of the insolublematerials by filtration, evaporation of the solvent gave complex A14 asa red solid (183.9 mg. yield 57.5%).

¹H NMR (C₆D₆) d1.25 (9H), 1.47 (9H), 1.69 (3H), 1.79 (3H), 6.29 (2H),6.95-8.42 (10H), 9.07 (1H)

³¹P NMR (C₆D₆) d9.60

ESI-MS (solvent: CH₃CN) 617 (M⁺CH₃CN-pyrole)

Examples of Polymerization Reaction Example A18

-   -   Toluene (5.0 mL) was added to an autoclave under nitrogen. After        stabilizing at 40° C., ethylene was fed while the ethylene        pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complex        A12 (0.10 μmol) were added to the autoclave, and the mixture was        allowed to polymerize for 20 minutes. The polymer was produced        at a rate of 6.4×10⁶ g per hour per 1 mole of titanium by the        polymerization reaction.

Example A19

A polymer was produced by the same method as in Example A18, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenyl borane (0.30 μmol) were usedin place of MMAO. The polymer was produced at a rate of 1.1×10⁶ g perhour per 1 mole of titanium by the polymerization reaction.

Example A20

A polymer was produced by the same method as in Example A18, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 3.4×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A21

A polymer was produced by the same method as in Example A18, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 4.4×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A22

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexA12 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 20 minutes. The polymer with a molecular weight (Mw)of 1.26×106, molecular weight distribution (Mw/Mn) of 4.4 and meltingpoint (Tm) of 126.7° C. was produced at a rate of 4.8×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example A23

A polymer was produced by the same method as in Example A22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 7.00×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example A24

A polymer was produced by the same method as in Example A22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.97×10⁷, a meltingpoint (Tm) of 124.7° C. and a number of branches of Me of 2 per 1,000carbon atoms was produced at a rate of 2.6×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example A25

A polymer was produced by the same method as in Example A22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 2.64×10⁶, molecularweight distribution (Mw/Mn) of 1.4, a melting point (Tm) of 121.4° C.and a number of branches of Me of 1 per 1,000 carbon atoms was producedat a rate of 3.6×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example A26

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexA12 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer with a molecular weight (Mw) of 1.42×10⁶,molecular weight distribution (Mw/Mn) of 4.1, melting point (Tm) of126.0° C. and a number of branches of Me of 7 per 1,000 carbon atoms wasproduced at a rate of 2.3×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example A27

A polymer was produced by the same method as in Example A26, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 2.29×10⁶, molecularweight distribution (Mw/Mn) of 2.2, a melting point (Tm) of 128.2° C.and a number of branches of Me of 2 per 1,000 carbon atoms was producedat a rate of 1.6×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example A28

A polymer was produced by the same method as in Example A26, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.26×10⁶, molecularweight distribution (Mw/Mn) of 1.5, a melting point (Tm) of 129.8° C.and a number of branches of Me of 8 per 1,000 carbon atoms was producedat a rate of 1.5×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example A29

Toluene (5.0 mL) and 1-hexene (40 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmol) and complexA12 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer was produced at a rate of 1.3×10⁶ g per hourper 1 mole of titanium by the polymerization reaction.

Example A30

A polymer was produced by the same method as in Example A29, except thata hexane solution of triisobutyl aluminum (4 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.030 μmol) were used in place ofMMAO. The polymer was produced at a rate of 8.00×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example A31

A polymer was produced by the same method as in Example A29, except thata hexane solution of triisobutyl aluminum (4 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 8.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example A32

Toluene (5.0 mL) was added to an autoclave under nitrogen and, afterstabilizing at 40° C., ethylene was added with compression and wasstabilized at 0.60 MPa. MMAO (100 μmol) and complex A13 (0.10 μmol) wereadded to the autoclave, and the mixture was allowed to polymerize. Thepolymer was produced at a rate of 2.7×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example A33

A polymer was produced by the same method as in Example A32, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 3.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example A34

A polymer was produced by the same method as in Example A32, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 2.3×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A35

A polymer was produced by the same method as in Example A32, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 2.6×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A36

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexA13 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer with a molecular weight (Mw) of 2.5×10⁶,molecular weight distribution (Mw/Mn) of 25.6 and a melting point (Tm)of 102.0° C. was produced at a rate of 2.2×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example A37

A polymer was produced by the same method as in Example A36, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenyl borane (0.30 μmol) were usedin place of MMAO. The polymer was produced at a rate of 3.00×10⁵ g perhour per 1 mole of titanium by the polymerization reaction.

Example A38

A polymer was produced by the same method as in Example A36, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 1.7×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A39

A polymer was produced by the same method as in Example A36, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate(0.30 μmol) were used in place of MMAO. The polymer with a molecularweight (Mw) of 2.89×10⁶, molecular weight distribution (Mw/Mn) of 8.4and a melting point (Tm) of 107.1° C. was produced at a rate of 1.9×10⁶g per hour per 1 mole of titanium by the polymerization reaction.

Example A40

Toluene (5.0 mL) was added to an autoclave under. After stabilizing at40° C., ethylene was fed while the ethylene pressure was adjusted at0.60 MPa. MMAO (100 μmmol) and complex A14 (0.10 μmol) were added to theautoclave, and the mixture was allowed to polymerize for 20 minutes. Thepolymer was produced at a rate of 4.5×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example A41

A polymer was produced by the same method as in Example A40, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 4.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example A42

A polymer was produced by the same method as in Example A40, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 5.0×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A43

A polymer was produced by the same method as in Example A40, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 6.2×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example A44

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen and, after stabilizing at 40° C., ethylene was added withcompression and was stabilized at 0.60 MPa. MMAO (100 μmmol) and complexA14 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer with a molecular weight (Mw) of 1.94×10⁶,molecular weight distribution (Mw/Mn) of 2.4 and a melting point (Tm) of123.0° C. was produced at a rate of 1.3×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example A45

A polymer was produced by the same method as in Example A44, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 2.00×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example A46

A polymer was produced by the same method as in Example A44, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 4.50×10⁶, molecularweight distribution (Mw/Mn) of 1.3 and a melting point (Tm) of 119.8° C.was produced at a rate of 4.2×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example A47

A polymer was produced by the same method as in Example A44, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 4.33×10⁶, molecularweight distribution (Mw/Mn) of 1.4 and a melting point (Tm) of 127.1° C.was produced at a rate of 4.3×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example B1 Synthesis of Compound B1

A 1.56 M solution of n-butyl lithium in hexane (14.1 mL) was drippedinto an ether solution (57.0 mL) of N,N-dimethylbenzylamine (2.70 g,20.0 mmol) at 0° C., and the reaction mixture was warmed to roomtemperature then stirred for 24 hours. The mixture was cooled to −78°C., and an ether solution (77.0 mL) of phosphorous trichloride (5.49 g,40.0 mmol) was added followed by warming to room temperature thenstirred for 2 hours. Compound B1 was quantitatively obtained by removingthe solvent from the filtrate in vacuum after removing insolublematerials by filtration.

¹H NMR (CD₂Cl₂) d2.46 (6H), 4.02 (2H), 7.29-8.53 (4H)

³¹P NMR (CD₂Cl₂) 115.6

Examples B2 Synthesis of Compound B2

A 1.56 M of n-butyl lithium solution in hexane (28.2 mL) was addeddropwise into a tetrahydrofuran solution (131.4 mL) of2-tert-butyl-1-methoxymethoxy-4-methylbenzene (8.33 g, 40 mmol) at −78C, and the mixture was warmed to room temperature then stirred for 1hour. The reaction mixture was cooled to −78° C., and a tetrahydrofuransolution (56.3 mL) of compound B1 (4.72 g, 20.0 mmol) was added followedby warming to room temperature with stirring for 10 hours. The reactionwas stopped by adding deionized water (100.0 mL) and toluene (100 mL).The organic layer was washed with saturated aqueous sodium chloridesolution (100 mL) followed by removing the solvent by evaporation toobtain a pale yellow oil as a desired product. The product was purifiedby silica gel column chromatography (hexane/ethyl acetate=10/1) toobtain compound B2 as a white solid (4.35 g, yield 37.5%).

¹H NMR (CDCl₃) d1.40 (18H), 2.09 (6H), 2.10 (6H), 3.50 (6H), 3.55 (2H),5.16-5.19 (4H), 6.35 (2H), 6.86-7.47 (6H)

MS 536 (M+1)

Example B3 Synthesis of Compound B2

A hexane solution (1.56 M) of n-butyl lithium was dripped into an ethersolution of N,N-dimethylbenzylamine at 0° C., and the solution is warmedto room temperature with stirring for 24 hours. The mixture is cooled to−78° C., and an ether solution of compound A1 is added followed bywarming to room temperature with stirring for 10 hours. Compound B2 isobtained by removing the solvent from the filtrate in vacuum afterremoving insoluble substances by filtration.

Example B4 Synthesis of Compound B3

Acetyl chloride (0.79 g, 10.0 mmol) was added to a solution of compoundB2 (0.95 g, 1.64 mol) in a mixed solvent (57.0 mL) of ethyl acetate andmethanol (1/1) at room temperature, and the solution was stirred at roomtemperature for 15 hours. Compound B3 was obtained as a white solid(403.5 mg, yield 49.8%) by removing the solvent by evaporation invacuum.

¹H NMR (CDCl₃) d1.41 (18H), 2.25 (6H), 3.01 (6H), 4.63 (2H), 6.31 (2H),7.06-8.81 (6H)

³¹P NMR (C₆D₆) d −26.9

Example B5 Synthesis of Complex B4

A toluene solution (6.70 mL) of titanium tetrachloride (0.40 g, 2.10mmol) was added dropwise into a toluene solution (6.70 mL) of compoundB2 (0.58 g, 1.00 mmol) at −78° C., and the mixture was stirred at roomtemperature for 10 hours. Complex B4 was quantitatively obtained as abrown solid by washing with pentane (2 mL) after removing the solvent bydistillation.

¹H NMR (C₆D₆) d1.59 (18H), 2.05 (6H), 2.41 (6H), 3.77 (2H), 6.84 (2H),6.99-7.89 (6H)

³¹P NMR (C₆D₆) d28.3

EI-MS 607 (M−1)

Example B6 Synthesis of Complex B5

A n-butyl lithium solution (1.56 M) in hexane (1.53 mL) was added into asolution of compound B3 (0.42 g, 0.80 mmol) in tetrahydrofuran (7.14 mL)at −78° C., and the mixture was warmed to room temperature with stirringfor 1 hour. The reaction mixture was added into a solution of zirconiumtetrachloride bis(tetrahydrofuran) complex (0.30 g, 0.80 mol) intetrahydrofuran (7.14 mL) at −78° C. After stirring the solution for 10hours at room temperature, 10.0 mL of toluene was added. Complex B5 wasobtained as a white solid (270 mg, yield 50%) by removing the solventfrom the filtrate in vacuum after removing insoluble materials byfiltration.

EI-MS: 649 (M−1)

Examples of Polymerization Reaction Example B7

Toluene (5.0 mL) was added in an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. Methylaluminoxane (100 μmol) and complex B4 (0.10μmmol) were added in the autoclave to polymerize the mixture for 5minutes. A polymer was produced at a rate of 3.62×10⁷ g per hour per 1mol of titanium by the polymerization reaction.

Example B8

A polymer was produced by the same method as in Example B6 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of methylaluminoxane. The polymer was produced at a rate of 6.00×10⁵ g per hourper 1 mol of titanium by polymerization.

Example B9

A polymer was produced by the same method as in Example B6 bypolymerization for 18 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer was produced at a rateof 6.90×10⁶ g per hour per 1 mol of titanium by polymerization.

Example B10

A polymer was produced by the same method as in Example B6 bypolymerization for 14 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer was produced at a rateof 8.80×10⁶ g per hour per 1 mol of titanium by polymerization.

Example B11

Toluene (5.0 mL) and 1-hexene (60 μL) were added in an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. Methyl aluminoxane (100μmol) and complex B4 (0.10 μmol) were added in the autoclave topolymerize the mixture for 9 minutes. A polymer was produced at a rateof 2.01×10⁷ g per hour per 1 mol of titanium by the polymerizationreaction.

Example B12

A polymer was produced by the same method as in Example B10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of methylaluminoxane. The polymer was produced at a rate of 5.00×10⁵ g per hourper 1 mol of titanium by polymerization.

Example B13

A polymer was produced by the same method as in Example B10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer with a molecular weight(Mw) of 1.97×10⁶, molecular weight distribution (Mw/Mn) of 1.6 and amelting point (Tm) of 117.9° C. was produced at a rate of 5.50×10⁶ g perhour per 1 mol of titanium by polymerization.

Example B14

A polymer was produced by the same method as in Example B10 bypolymerization for 14 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer with a molecular weight(Mw) of 7.61×10⁶, molecular weight distribution (Mw/Mn) of 1.6 and amelting point (Tm) of 113.1° C. was produced at a rate of 1.04×10⁷ g perhour per 1 mol of titanium by polymerization.

Example B15

Toluene (5.0 mL) was added in an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. Methylaluminoxane (100 μmol) and complex B5 (0.10μmmol) were added in the autoclave to polymerize the mixture for 20minutes. A polymer was produced at a rate of 4.90×10⁶ g per hour per 1mol of titanium by the polymerization reaction.

Example B16

A polymer was produced by the same method as in Example B14, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of methyl aluminoxane. The polymer was produced at a rate of3.00×10⁵ g per hour per 1 mol of zirconium by polymerization.

Example B17

A polymer was produced by the same method as in Example B14 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer was produced at a rateof 5.50×10⁶ g per hour per 1 mol of zirconium by polymerization.

Example B18

A polymer was produced by the same method as in Example B14 bypolymerization for 17 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer was produced at a rateof 7.30×10⁶ g per hour per 1 mol of zirconium by polymerization.

Example B19

Toluene (5.0 mL) and 1-hexene (60 μL) were added in an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. Methyl aluminoxane (100μmol) and complex B5 (0.10 μmol) were added in the autoclave topolymerize the mixture for 20 minutes. A polymer with a molecular weight(Mw) of 2.40×10⁵, molecular weight distribution (Mw/Mn) of 31.2 and amelting point (Tm) of 130.6° C. was produced at a rate of 4.60×10⁶ g perhour per 1 mol of zirconium by the polymerization reaction.

Example B20

A polymer was produced by the same method as in Example B18 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of methylaluminoxane. The polymer was produced at a rate of 4.00×10⁵ g per hourper 1 mol of zirconium by polymerization.

Example B21

A polymer was produced by the same method as in Example B18 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer with a molecular weight(Mw) of 4.00×10³, molecular weight distribution (Mw/Mn) of 1.4, amelting point (Tm) of 127.6° C. and a number of branches of Me per 1000carbon atoms of 13 was produced at a rate of 5.10×10⁶ g per hour per 1mol of zirconium by the polymerization reaction.

Example B22

A polymer was produced by the same method as in Example B18 bypolymerization for 11 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of methyl aluminoxane. The polymer with a molecular weight(Mw) of 4.50×10³, molecular weight distribution (Mw/Mn) of 1.5, amelting point (Tm) of 129.3° C. and a number of branches of Me per 1000carbon atoms of 20 was produced at a rate of 1.03×10⁷ g per hour per 1mol of zirconium by the polymerization reaction.

Example C1 Synthesis of Compound C1

Sodium borohydride (0.03 g, 0.83 mmol) was added to an ethanol solution(5.76 mL) of compound A6 (0.45 g, 0.75 mmol) at room temperature, andthe mixture was stirred for 2 hours. The reaction was stopped by addingdeionized water (10.0 mL) and toluene (10.0 mL). After washing theseparated organic layer with a saturated aqueous solution (10.0 mL) ofsodium chloride, the solvent was removed by evaporation toquantitatively obtain compound C1 as a white solid.

¹H NMR (CDCl₃) d0.98 (9H), 1.32 (18H), 2.03 (6H), 3.38 (6H), 3.3 (2H),5.05 (4H), 6.35 (2H), 6.78 (2H), 7.01-7.20 (4H), 7.37 (1H)

Example C2 Synthesis of Compound C2

Acetyl chloride (0.32 g, 4.03 mmol) was added to a solution (20.0 mL) ofcompound C5 (0.49 g, 0.81 mmol) in a mixed solvent (20.0 mL) of ethylacetate and methanol (1/1) at room temperature, and the mixture wasstirred for 15 minutes. Compound C2 was obtained as a white solid (345.0mg, yield 76.7%) by removing the solvent by evaporation in vacuum.

¹H NMR (CDCl₃) d1.21 (9H), 1.40 (18H), 2.13 (6H), 3.87 (2H), 6.38 (2H),7.01-7.37 (5H), 7.71 (1H), 9.26 (2H)

Example C3 Synthesis of Compound C3

Sodium chloride is added to a tetrahydrofuran solution of compound C6with stirring. The reaction is stopped by adding deionized solution, theorganic layer is separated and compound C3 is obtained by removing thesolvent by evaporation.

Example C4 Synthesis of Complex C4

A tetrahydrofuran solution (3.11 mL) of compound C6 (0.35 g, 0.62 mmolwas added into a tetrahydrofuran solution (2.33 mL) of 60% sodiumhydride (0.15 g, 3.72 mmol) at −78° C., and the mixture was warmed toroom temperature and then stirred for 1 hour. The reaction mixture wasadded into a tetrahydrofuran solution (2.33 mL) of titaniumtetrachloride bis(tetrahydrofuran) complex (0.21 g, 0.62 mmol) at −78°C. The solution was warmed to room temperature with stirring for 10hours, and toluene (5.0 mL) was added after removing the solvent byevaporation in vacuum. Complex C4 (258.5 mg, 61.5%) was obtained as ared solid by removing the solvent form the filtrate in vacuum afterremoving insoluble materials by filtration.

¹H NMR (C₆D₆) d0.88 (9H), 1.34 (18H), 1.68 (6H), 3.80 (2H), 6.60-7.88(8H)

EI-MS 600 (M⁺)

Examples of Polymerization Reaction Example C5

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. MMAO (100 μmmol) and complex C4 (0.10 μmol) wereadded to the autoclave, and the mixture was allowed to polymerize for 20minutes. The polymer was produced at a rate of 3.4×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example C6

A polymer was produced by the same method as in Example C5, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenyl borane (0.30 μmol) were usedin place of MMAO. The polymer was produced at a rate of 1.3×10⁶ g perhour per 1 mole of titanium by the polymerization reaction.

Example C7

A polymer was produced by the same method as in Example C5, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 mmol) were used in place ofMMAO. The polymer was produced at a rate of 3.1×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example C8

A polymer was produced by the same method as in Example C5, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 5.0×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example C9

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexC4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 20 minutes. The polymer with a molecular weight (Mw)of 1.39×10⁶, molecular weight distribution (Mw/Mn) of 8.1 and meltingpoint (Tm) of 122.6° C. was produced at a rate of 3.0×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example C10

A polymer was produced by the same method as in Example C9, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer with a molecular weight (Mw) of 1.84×10⁶,molecular weight distribution (Mw/Mn) of 19.0 and melting point (Tm) of124.5° C. was produced at a rate of 2.1×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example C11

A polymer was produced by the same method as in Example C9, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.94×10⁶, molecularweight distribution (Mw/Mn) of 48.7, melting point (Tm) of 122.9° C. anda number of branches of Me per 1000 carbon atoms of 3 was produced at arate of 2.6×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Example C12

A polymer was produced by the same method as in Example C9, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 3.22×10⁶, molecularweight distribution (Mw/Mn) of 241.9, and melting point (Tm) of 120.6°C. was produced at a rate of 4.5×10⁶ g per hour per 1 mole of titaniumby the polymerization reaction.

Example C13

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexC4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 20 minutes. The polymer with a molecular weight (Mw)of 1.51×10⁶, molecular weight distribution (Mw/Mn) of 3.4 and meltingpoint (Tm) of 128.0° C. was produced at a rate of 2.3×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example C14

A polymer was produced by the same method as in Example C13, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 3.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example C15

A polymer was produced by the same method as in Example C13, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.57×10⁶, molecularweight distribution (Mw/Mn) of 4.3, and melting point (Tm) of 121.0° C.was produced at a rate of 2.3×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example C16

A polymer was produced by the same method as in Example C13, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 8.0×10⁵, molecularweight distribution (Mw/Mn) of 2.2, and melting point (Tm) of 120.4° C.was produced at a rate of 2.00×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example C17

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmol) and complexC4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer was produced at a rate of 9.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example C18

A polymer was produced by the same method as in Example C17, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 2.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example C19

A polymer was produced by the same method as in Example C17, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 1.20×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example C20

A polymer was produced by the same method as in Example C17, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 7.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example C21

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 mol) and complexC4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 20 minutes. The polymer with a molecular weight (Mw)of 1.5×10⁶, molecular weight distribution (Mw/Mn) of 3.4, and meltingpoint (Tm) of 118.0° C. was produced at a rate of 2.3×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example C22

A polymer was produced by the same method as in Example C21, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 3.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example C23

A polymer was produced by the same method as in Example C21, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.6×10⁶, molecularweight distribution (Mw/Mn) of 4.3, and melting point (Tm) of 121.0° C.was produced at a rate of 2.3×10⁵ g per hour per 1 mole of titanium bythe polymerization reaction.

Example C24

A polymer was produced by the same method as in Example C21, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 8.0×10⁵, molecularweight distribution (Mw/Mn) of 2.2 and melting point (Tm) of 120.4° C.was produced at a rate of 2.0×10⁵ g per hour per 1 mole of titanium bythe polymerization reaction.

Example C25

Toluene (5.0 mL) and 1-hexene (40 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was added withcompression and was stabilized at 0.60 MPa. MMAO (100 μmmol) and complexC4 (0.10 mol) were added to the autoclave, and the mixture was allowedto polymerize for 5 minutes. The polymer was produced at a rate of9.0×10⁵ g per hour per 1 mole of titanium by the polymerizationreaction.

Example C26

A polymer was produced by the same method as in Example C25, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 2.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example C27

A polymer was produced by the same method as in Example C25, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borane (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 1.2×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example C28

A polymer was produced by the same method as in Example C25, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borane (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 7.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example D1 Synthesis of Compound D1

Sodium borohydride (0.95 g, 25.0 mmol) was added to a solution ofcompound A4 (2.75 g, 5.0 mmol) in ethanol (350 mL) at room temperature,and the mixture was stirred for 3 hours. The reaction was stopped byadding deionized water (100.0 mL) and toluene (100.0 mL), and theorganic layer was washed with a saturated aqueous solution (70 mL) ofsodium chloride followed by drying the organic layer over sodiumsulfate. A crude product was obtained as a yellow oil by removing thesolvent by evaporation. The crude product was purified by silica gelcolumn chromatography (hexane/ethyl acetate=10/1→4/1) to obtain compoundD as a white solid (2.00 g, yield 74.1%).

¹H NMR (CDCl₃) d1.39 (18H), 2.12 (6H), 3.47 (6H), 4.80 (2H), 5.16-5.21(4H), 6.35 (2H), 6.90 (1H), 7.14-7.61 (5H)

Example D2 Synthesis of Compound D2

Acetyl chloride (0.64 g, 8.14 mmol) was added to a solution of compoundD1 (1.5 g, 2.71 mmol) in a 1/1 mixed solvent (60.0 mL) of ethyl acetateand methanol at room temperature and the mixture was stirred for 15hours. Compound D2 was obtained as a white solid (1.06 g, yield 84.5%)by removing the solvent by evaporation in vacuum

¹H NMR (C₆D₆) d1.46 (18H), 1.82 (6H), 5.07 (2H), 6.17-7.32 (8H), 9.38(2H)

MS Spectrum (EI) 464 (M+)

Example D3 Synthesis of Transition Metal Complex

A 1.57 M hexane solution (1.91 mL) of n-butyl lithium was added dropwiseinto a tetrahydrofuran solution (7.85 mL) of compound D2 (0.46 g, 1.00mmol) at −78° C., and the reaction mixture was warmed to roomtemperature then stirred for 1 hour. The mixed reaction solution wasdripped into a tetrahydrofuran solution (7.85 mL) of titaniumtetrachloride bis(tetrahydrofuran) complex (0.33 g, 1.00 mmol) at −78°C. The solution was warmed to room temperature and the mixture wasstirred for 10 hours. After removing the solvent by evaporation invacuum, toluene (10.0 mL) was added and insoluble materials were removedby filtration. The transition metal complex was obtained as a red solid(330 mg) by removing the solvent from the filtrate in vacuum.

³¹P NMR (C₆D₆) δ-1.18

MS spectrum (EI) 971

Example of Polymerization Reaction Example D4

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. MMAO (100 μmol) and transition metal complex D3(0.10 μmol) obtained in Example D3 were added to the autoclave, and themixture was allowed to polymerize for 20 minutes. The polymer wasproduced at a rate of 6.8×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example D5

A polymer was produced by the same method as in Example D4, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenyl borane (0.30 μmol) were usedin place of MMAO. The polymer was produced at a rate of 1.0×10⁵ g perhour per 1 mole of titanium by the polymerization reaction.

Example D6

A polymer was produced by the same method as in Example D4, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylanilinium tetrakis(pentafluorophenylborate (0.30 μmol) were used in place of MMAO. The polymer was producedat a rate of 3.0×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example D7

A polymer was produced by the same method as in Example D4, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyl tetrakis(pentafluorophenylborate (0.30 μmol) were used in place of MMAO. The polymer was producedat a rate of 3.2×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example D8

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) andtransition metal complex (0.10 μmol) obtained in Example D3 were addedto the autoclave, and the mixture was allowed to polymerize for 20minutes. The polymer with a molecular weight (Mw) of 3.1×10⁶, molecularweight distribution (Mw/Mn) of 2.6 and melting point (Tm) of 104.7° C.was produced at a rate of 5.7×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example D9

A polymer was produced by the same method as in Example D8, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 1.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example D10

A polymer was produced by the same method as in Example D8, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 5.3×10⁵, molecularweight distribution (Mw/Mn) of 10.1 and melting point (Tm) of 135.5° C.was produced at a rate of 2.6×16 g per hour per 1 mole of titanium bythe polymerization reaction.

Example D11

A polymer was produced by the same method as in Example D8, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.7×10⁶, molecularweight distribution (Mw/Mn) of 22.8 and melting point (Tm) of 118.0° C.was produced at a rate of 2.7×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example D12

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmol) andtransition metal complex (0.10 μmol) obtained in Example D3 were addedto the autoclave, and the mixture was allowed to polymerize for 20minutes. The polymer with a molecular weight (Mw) of 2.1×10⁶, molecularweight distribution (Mw/Mn) of 5.1 and melting point (Tm) of 115.5° C.was produced at a rate of 4.4×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example D13

A polymer was produced by the same method as in Example D12, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 mmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 6.9×10⁵, molecularweight distribution (Mw/Mn) of 19.7 and melting point (Tm) of 118.8° C.was produced at a rate of 9.0×10⁵ g per hour per 1 mole of titanium bythe polymerization reaction.

Example D14

A polymer was produced by the same method as in Example D12, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 8.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example D15

Toluene (5.0 mL) and 1-hexene (40 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) andtransition metal complex (0.10 μmol) obtained in Example D3 were addedto the autoclave, and the mixture was allowed to polymerize for 5minutes. The polymer was produced at a rate of 6.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example D16

A polymer was produced by the same method as in Example D15, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 3.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example D17

A polymer was produced by the same method as in Example D15, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 6.0×10⁵ g per hour per 1mole of titanium by the polymerization reaction.

Example E1 Synthesis of Compound E1

A n-butyl lithium solution of (1.56 M) in n-hexane (21.2 mL) was addeddropwise into a solution of pentafluorobromobenzene (7.41 g, 30.0 mmol)in diethylether (116.8 mL) at −78° C. and the mixture was stirred for 1hour. A diethylether solution (50.0 mL) of compound A1 (14.43 g, 30.0mmol) was added to the mixture, and the resulting mixture was warmed toroom temperature with stirring for 5 hours. The reaction was stopped byadding deionized water (100 mL) and toluene (100 mL). After washing theorganic layer with a saturated aqueous solution (100 mL) of sodiumchloride, the solvent was removed by evaporation to obtain compound E1as a white solid (17.9 g, yield 98.0%).

¹H NMR (CDCl₃) δ 3.40 (18H), 2.18 (6H), 3.50 (6H), 5.18-5.28 (4H), 6.53(2H), 7.19 (2H)

³¹P NMR (C₆D₆) δ-30.7

Example E2 Synthesis of Compound E1

A 1.56 M hexane solution of n-butyl lithium is added dropwise into adiethyl ether solution of 2-tert-butyl-1-methoxy-4-methylbenzene at −78°C. and the mixture was stirred for 1 hour. A diethylether solution ofpentafluorophenyl dichlorophosphine is added into the mixed reactionsolution, and the solution is warmed to room temperature with stirring.Compound E1 can be obtained by applying the same post-treatment as inExample E1.

Example E3 Synthesis of Compound E2

Acetyl chloride (2.65 g, 33.8 mmol) was added to a solution of compoundE1 (4.14 g, 6.76 mmol) in a mixed solvent (65.0 mL) ofethylacetate/methanol (1/1) at room temperature with stirring for 15hours. Compound E2 was obtained as a white solid (2.55 g, yield 72.0%)by removing the solvent by evaporation in vacuum.

¹H NMR (CDCl₃) δ 1.40 (18H), 2.21 (6H), 6.81 (2H), 7.17 (2H)

³¹P NMR (C₆D₆) δ-59.6

¹⁹F NMR (C₆D₆) δ-161.5, −151.3, −130.7

Example E4 Synthesis of Complex E3

A toluene solution of titanium tetrachloride (0.11 g, 0.60 mmol) wasdripped into a toluene solution (3.54 mL) of compound E1 (0.31 g, 0.50mmol), and the solution was warmed to room temperature followed bystirring for 10 hours. Compound E3 was obtained as a red solid (208.7mg, yield 65.2%) by removing the solvent from the filtrate afterfiltrating insoluble materials.

¹H NMR (C₆D₆) δ 1.35-1.44 (18H), 1.84-2.01 (6H), 6.89-7.01 (4H)

³¹P NMR (C₆D₆) δ 0.36

¹⁹F NMR (C₆D₆) δ-161.0, −149.1, −123.1

EI-MS 640 (M−1)

Example E5 Synthesis of Complex E4

A 1.56 M hexane solution (1.03 mL) of n-butyl lithium was added dropwiseinto a tetrahydrofuran solution (4.73 mL) of compound E2 (0.46 g, 0.80mmol) at −78° C., and the reaction mixture was warmed to roomtemperature then stirred for 1 hour. The reaction mixture was added intoa tetrahydrofuran solution (10.0 mL) of zirconium tetrachloridebis(tetrahydrofuran) complex (0.30 g, 0.80 mmol). The mixture was warmedto room temperature with stirring for 10 hours. After warming thesolution to room temperature with stirring for 10 hours and removing thesolvent by evaporation in vacuum, toluene (5.0 mL) was added to theresidue. Complex E4 was obtained as a white solid (249.5 mg, yield45.4%) by removing the solvent from the filtrate after removinginsoluble materials by filtration.

¹H NMR (CD₂Cl₂) δ 1.31 (18H), 2.21 (6H), 6.93 (2H), 7.09 (2H)

³¹P NMR (CD₂Cl₂) δ-19.5

¹⁹F NMR (CD₂Cl₂) δ-161.6, −151.4, −124.1

EI-MS 684 (M+)

Example of Polymerization Reaction Example E6

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. MMAO (100 μmmol) and transition metal complex(0.10 μmol) obtained in Example E3 were added to the autoclave, and themixture was allowed to polymerize for 3 minutes. The polymer wasproduced at a rate of 5.99×10⁷ g per hour per 1 mole of titanium by thepolymerization reaction.

Example E7

A polymer was produced by the same method as in Example E6, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 1.3×10⁶ g per hourper 1 mole of titanium by the polymerization reaction.

Example E8

A polymer was produced by the same method as in Example E6 bypolymerization for 5 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer was produced at a rate of 3.43×10⁷ gper hour per 1 mole of titanium by the polymerization reaction.

Example E9

A polymer was produced by the same method as in Example E6 bypolymerization for 3.5 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer was produced at a rate of 4.90×10⁷ gper hour per 1 mole of titanium by the polymerization reaction.

Example E10

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexE3 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 3.6 minutes. The polymer with a molecular weight (Mw)of 7.3×10⁴, molecular weight distribution (Mw/Mn) of 2.7, a meltingpoint (Tm) of 118.2° C. and a number of branching of Me per 1,000 atomsof 7 was produced at a rate of 4.52×10⁷ g per hour per 1 mole oftitanium by the polymerization reaction.

Example E11

A polymer was produced by the same method as in Example E10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of MMAO. Thepolymer with a molecular weight (Mw) of 2.5×10⁴, molecular weightdistribution (Mw/Mn) of 2.1, a melting point (Tm) of 117.6° C. and anumber of branching of Me per 1,000 atoms of 4 was produced at a rate of1.70×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Example E12

A polymer was produced by the same method as in Example E10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer with a molecular weight (Mw) of3.60×10⁴, molecular weight distribution (Mw/Mn) of 1.8, a melting point(Tm) of 117.2° C. and a number of branching of Me per 1,000 atoms of 16was produced at a rate of 6.02×10⁷ g per hour per 1 mole of titanium bythe polymerization reaction.

Example E14

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmol) and complexE3 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 13 minutes. The polymer with a molecular weight (Mw)of 5.6×10⁴, molecular weight distribution (Mw/Mn) of 2.3 and a meltingpoint (Tm) of 127.0° C. was produced at a rate of 5.5×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example E15

A polymer was produced by the same method as in Example E14 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of MMAO. Thepolymer with a molecular weight (Mw) of 2.8×10⁵, molecular weightdistribution (Mw/Mn) of 3.4, a melting point (Tm) of 132.0° C. and anumber of branching of Me per 1,000 atoms of 1 was produced at a rate of1.00×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Example E16

A polymer was produced by the same method as in Example E14 bypolymerization for 6 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer with a molecular weight (Mw) of4.9×10⁴, molecular weight distribution (Mw/Mn) of 2.3, a melting point(Tm) of 129.0° C. and a number of branching of Me per 1,000 atoms of 6was produced at a rate of 1.62×10⁷ g per hour per 1 mole of titanium bythe polymerization reaction.

Example E17

A polymer was produced by the same method as in Example E14 bypolymerization for 6 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer with a molecular weight (Mw) of3.60×10⁴, molecular weight distribution (Mw/Mn) of 1.8, a melting point(Tm) of 128.0° C. and a number of branching of Me per 1,000 atoms of 8was produced at a rate of 1.15×10⁷ g per hour per 1 mole of titanium bythe polymerization reaction.

Example E18

Toluene (5.0 mL) and 1-hexene (40 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexE3 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 5 minutes. The polymer was produced at a rate of8.0×10⁵ g per hour per 1 mole of titanium by the polymerizationreaction.

Example E19

A polymer was produced by the same method as in Example E18 bypolymerization for 6 minutes, except that a hexane solution oftriisobutyl aluminum (4 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.030 μmol) were used in place of MMAO. Thepolymer was produced at a rate of 2.00×10⁷ g per hour per 1 mole oftitanium by the polymerization reaction.

Example E20

A polymer was produced by the same method as in Example E18 bypolymerization for 6 minutes, except that a hexane solution oftriisobutyl aluminum (4 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.030 μmol)were used in place of MMAO. The polymer was produced at a rate of8.00×10⁵ g per hour per 1 mole of titanium by the polymerizationreaction.

Example E21

A polymer was produced by the same method as in Example E18 bypolymerization for 6 minutes, except that a hexane solution oftriisobutyl aluminum (4 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.030 μmol) wereused in place of MMAO. The polymer was produced at a rate of 2.0×10⁵ gper hour per 1 mole of titanium by the polymerization reaction.

Example E22

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. MMAO (100 μmol) and complex E4 (0.10 μmol) wereadded to the autoclave, and the mixture was allowed to polymerize for 20minutes. The polymer was produced at a rate of 2.6×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example E23

A polymer was produced by the same method as in Example E22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 5.0×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example E24

A polymer was produced by the same method as in Example E22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 mmol) were used in place ofMMAO. The polymer was produced at a rate of 7.6×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example E25

A polymer was produced by the same method as in Example E22, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 1.85×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example E26

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexE4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize. The polymer with a molecular weight (Mw) of 3.20×10⁵ andmolecular weight distribution (Mw/Mn) of 46.5 was produced at a rate of1.9×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Example E27

A polymer was produced by the same method as in Example E26, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. The polymer was produced at a rate of 3.00×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Example E28

A polymer was produced by the same method as in Example E26, except thata hexane solution of triisobutyl aluminum (40 μL, 1.0 M, manufactured byKanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 8.0×10³, molecularweight distribution (Mw/Mn) of 1.6 and a number of branches of Me per1,000 carbon atoms of 42 was produced at a rate of 8.6×10⁶ g per hourper 1 mole of titanium by the polymerization reaction.

Example E29

A polymer was produced by the same method as in Example E26 bypolymerizing for 8 minutes, except that a hexane solution of triisobutylaluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.) andtriphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) were usedin place of MMAO. The polymer with a molecular weight (Mw) of 8.6×10³,molecular weight distribution (Mw/Mn) of 1.6 and a number of branches ofMe per 1,000 carbon atoms of 40 was produced at a rate of 2.51×10⁷ g perhour per 1 mole of titanium by the polymerization reaction.

Example F1 Synthesis of Compound F1

A 1.57 M solution (33.4 mL) of n-butyl lithium was added dropwise intoan ether solution (77.3 mL) of 2-N,N-dimethylamino-1-bromobenzene (10.0g, 50.0 mmol) at −78° C., and the mixture was warmed to room temperaturethen stirred for 1 hour. The solution was cooled to −78° C., and anether solution (51.0 mL) of compound A1 (24.1 g, 50.0 mmol) was added tothe solution followed by warming to room temperature then the resultingmixture was stirred for 3 hours. The reaction was stopped by addingdeionized water (100.0 mL) and toluene (100.0 mL). After washing theorganic layer with saturated aqueous sodium chloride solution (100 mL),the solvent was removed by evaporation to obtain a desired product as apale yellow oil. The product was purified by silica gel columnchromatography, and compound F1 was obtained as a white solid (13.27 g,yield 46.9%).

¹H NMR (CDCl₃) δ 1.41 (18H), 2.10 (6H), 2.54 (6H), 3.52 (6H), 5.25-5.34(4H), 6.29 (2H), 6.81-7.30 (6H)

Example F2 Synthesis of Compound F2

Acetyl chloride (5.89 g, 75.0 mmol) was added to a solution (340 mL) ofcompound F1 (8.49 g, 15.0 mmol) in a mixed solvent of ethylacetate/methanol (1/1). Compound F2 was quantitatively obtained as awhite solid by removing the solvent by evaporation in vacuum.

¹H NMR (CDCl₃) δ 1.38 (18H), 2.10 (6H), 3.11 (6H), 6.46 (2H), 7.19-7.66(6H)

³¹P NMR (CD₂Cl₂) δ-52.2

Example 3 Synthesis of Compound F3

A 1.57 M solution of n-butyl lithium is added dropwise into atetrahydrofuran solution of 2-N,N-dimethylamino-1-bromobenzene at −78°C., and the solution was warmed to room temperature and the mixture isstirred for 1 hour. The reaction mixture is dripped into atetrahydrofuran solution of phosphorous trichloride at −78° C., and themixture is warmed to room temperature then stirred for 5 hours. CompoundF3 is obtained by removing the solvent from the filtrate by evaporationin vacuum after removing insoluble materials by filtration.

Example F4 Synthesis of Compound F1

A 1.56 M hexane solution of n-butyl lithium is added dropwise into atetrahydrofuran solution of 1-methoxy-2-tert-butyl-4-methylbenzene at−78° C., and the reaction mixture is warmed to room temperature thenstirred for 1 hour. A tetrahydrofuran solution of compound F3 is addedinto the reaction mixture at −78° C., and the mixture is warmed to roomtemperature then stirred for 10 hours. Compound F1 is obtained byapplying a same post-treatment as in Example F1.

Example F5 Synthesis of Complex F4

A toluene solution (8.44 mL) of titanium tetrachloride (0.29 g, 1.55mmol) was added dropwise into a toluene solution (8.44 mL) of compoundF1 (0.73 g, 1.29 mmol) at −78° C., and the mixture was warmed to roomtemperature then stirred for 10 hours. Complex F4 was obtained as a redbrown solid (270 mg, yield 35.1%) by removing the solvent from thefiltrate by evaporation in vacuum after removing insoluble materials byfiltration.

³¹P NMR (CD₂Cl₂): δ 26.0

EI-MS: 560 (M-Cl)

Example of Polymerization Reaction Example F6

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. MMAO (100 μmmol) and complex F4 (0.10 μmol) wereadded to the autoclave, and the mixture was allowed to polymerize for8.5 minutes. The polymer was produced at a rate of 1.60×10⁷ g per hourper 1 mole of titanium by the polymerization reaction.

Example F7

A polymer was produced by the same method as in Example F6 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of MMAO. Thepolymer was produced at a rate of 2.00×10⁵ g per hour per 1 mole oftitanium by the polymerization reaction.

Example F8

A polymer was produced by the same method as in Example F6 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of MMAO. Thepolymer was produced at a rate of 3.0×10⁶ g per hour per 1 mole oftitanium by the polymerization reaction.

Example F9

A polymer was produced by the same method as in Example F6 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer was produced at a rate of 3.0×10⁶ gper hour per 1 mole of titanium by the polymerization reaction.

Example F10

Toluene (5.0 mL) and 1-hexene (60 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmol) and complexF4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 7 minutes. The polymer with a molecular weight (Mw) of1.20×10⁶, molecular weight distribution (Mw/Mn) of 99.1 and a number ofbranches of Me per 1,000 carbon atoms of 6 was produced at a rate of1.630×10⁷ g per hour per 1 mole of titanium by the polymerizationreaction.

Example F11

A polymer was produced by the same method as in Example F10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and pentafluorophenylborane (0.30 μmol) were used in place of MMAO. Thepolymer was produced at a rate of 2.00×10⁵ g per hour per 1 mole oftitanium by the polymerization reaction.

Example F12

A polymer was produced by the same method as in Example F10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer with a molecular weight (Mw) of1.69×10⁶ and molecular weight distribution (Mw/Mn) of 14.0 was producedat a rate of 1.90×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example F13

A polymer was produced by the same method as in Example F10 bypolymerization for 20 minutes, except that a hexane solution oftriisobutyl aluminum (40 μL, 1.0 M, manufactured by Kanto Chemical Co.)and triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) wereused in place of MMAO. The polymer with a molecular weight (Mw) of2.18×10⁶ and molecular weight distribution (Mw/Mn) of 8.0 was producedat a rate of 1.90×10⁶ g per hour per 1 mole of titanium by thepolymerization reaction.

Example F14

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 70° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexF4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 20 minutes. The polymer with a molecular weight (Mw)of 8.1×10⁵, molecular weight distribution (Mw/Mn) of 5.9 and a meltingpoint (Tm) of 116.9° C. was produced at a rate of 1.7×10⁶ g per hour per1 mole of titanium by the polymerization reaction.

Example F15

A polymer was produced by the same method as in Example F14 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 9.3×10⁵, molecularweight distribution (Mw/Mn) of 8.9 and melting point (Tm) of 120.6° C.was produced at a rate of 1.4×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example F16

A polymer was produced by the same method as in Example F14 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer with a molecular weight (Mw) of 1.0×10⁶, molecularweight distribution (Mw/Mn) of 5.6 and melting point (Tm) of 119.3° C.was produced at a rate of 1.4×10⁶ g per hour per 1 mole of titanium bythe polymerization reaction.

Example F17

Toluene (5.0 mL) and 1-hexene (40 μL) were added to an autoclave undernitrogen. After stabilizing at 130° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. MMAO (100 μmmol) and complexF4 (0.10 μmol) were added to the autoclave, and the mixture was allowedto polymerize for 5 minutes. The polymer was produced at a rate of1.1×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Example F18

A polymer was produced by the same method as in Example F17 bypolymerization, except that a hexane solution of triisobutyl aluminum (4μL, 1.0 M, manufactured by Kanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 6.0×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Example F19

A polymer was produced by the same method as in Example F17 bypolymerization, except that a hexane solution of triisobutyl aluminum (4μL, 1.0 M, manufactured by Kanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. The polymer was produced at a rate of 7.0×10⁶ g per hour per 1mole of titanium by the polymerization reaction.

Comparative Example 1

Toluene (5.0 mL) was added to an autoclave under nitrogen. Afterstabilizing at 40° C., ethylene was fed while the ethylene pressure wasadjusted at 0.60 MPa. Methyl aluminoxane (100 mmol) and2,2′-(phenylphosphine)bis(6-tert-butyl-4-methylphenoxy)(tetrahydrofuran)titaniumdichloride (0.10 μmol) were added to the autoclave, and the mixture wasallowed to polymerize for 30 minutes. The polymer was produced at a rateof 1.00×10⁶ g per hour per 1 mole of titanium by the polymerizationreaction.

Comparative Example 2

A polymer was produced by the same method as in Comparative Example 1 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) andpentafluorophenylborane (0.30 μmol) were used in place of methylaluminoxane. The polymer was produced at a rate of 3.00×10⁵ g per hourper 1 mole of titanium by the polymerization reaction.

Comparative Example 3

A polymer was produced by the same method as in Comparative Example 1 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofmethyl aluminoxane. The polymer was produced at a rate of 1.20×10⁶ g perhour per 1 mole of titanium by the polymerization reaction.

Comparative Example 4

A polymer was produced by the same method as in Comparative Example 1 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofmethyl aluminoxane. The polymer was produced at a rate of 1.30×10⁶ g perhour per 1 mole of titanium by the polymerization reaction.

Comparative Example 5

Toluene (5.0 mL) and 1-hexene (50 μL) were added to an autoclave undernitrogen. After stabilizing at 40° C., ethylene was fed while theethylene pressure was adjusted at 0.60 MPa. Methyl aluminoxane (100μmol) and2,2′-(phenylphosphine)bis(6-tert-butyl-4-methylphenoxy)(tetrahydrofuran)titaniumdichloride (0.10 μmol) were added to the autoclave, and the mixture wasallowed to polymerize for 30 minutes. The polymer was produced at a rateof 5.00×10⁵ g per hour per 1 mole of titanium by the polymerizationreaction.

Comparative Example 6

A polymer was produced by the same method as in Comparative Example 5 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofmethyl aluminoxane. The polymer was produced at a rate of 6.00×10⁵ g perhour per 1 mole of titanium by the polymerization reaction.

Comparative Example 6

A polymer was produced by the same method as in Comparative Example 5 bypolymerization, except that a hexane solution of triisobutyl aluminum(40 μL, 1.0 M, manufactured by Kanto Chemical Co.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofmethyl aluminoxane. The polymer was produced at a rate of 7.00×10⁵ g perhour per 1 mole of titanium by the polymerization reaction.

INDUSTRIAL APPLICABILITY

The transition metal complex having the ligand of the invention isuseful as a component of a catalyst for polymerizing olefins. Thecatalyst has a good polymerization activity and is capable of being usedfor production of high molecular weight olefin polymers.

1. A phosphine compound of formula (1):

wherein R¹, R², R³, R⁴, R⁶, R⁷ and R⁸ are the same or different, andindependently represent, a hydrogen atom, a halogen atom, a substitutedor unsubstituted alkyl group having 1 to 10 carbon atom(s), asubstituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, asilyl group substituted with a substituted or unsubstituted hydrocarbonhaving 1 to 20 carbon atom(s), a substituted or unsubstituted alkoxygroup having 1 to 10 carbon atom(s), a substituted or unsubstitutedaralkyloxy group having 7 to 20 carbon atoms, a substituted orunsubstituted aryloxy group having 6 to 20 carbon atoms, or an aminogroup disubstituted with hydrocarbons having 1 to 20 carbon atom(s); R⁵represents, a hydrogen atom, a fluorine atom, a substituted orunsubstituted alkyl group having 1 to 10 carbon atom(s), a substitutedor unsubstituted aralkyl group having 7 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms, ora silyl group substituted with a substituted or unsubstitutedhydrocarbon having 1 to 20 carbon atoms, G¹ represents a hydrogen atomor a protective group of hydroxyl group; G² represents any one of G²¹ toG²⁶ below,

wherein A¹ represents an element of Group 15 of the periodic table, andA² represents an element of Group 16 of the periodic table, and A¹ inG²¹ represents a nitrogen atom; R⁹ and R¹⁴ each represents a substitutedor unsubstituted alkyl group having 1 to 10 carbon atom(s), asubstituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,or a group of formula:R⁹⁰—N—R⁹¹ wherein R⁹⁰ and R⁹¹ are the same or different, and represent asubstituted or unsubstituted alkyl group having 1 to 10 carbon atom(s),a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, a substituted or unsubstituted aryl group having 6 to 20 carbonatoms, or a cyclic structure by being linked together, R¹², R¹³, R¹⁹ andR²⁰ each independently represents, a substituted or unsubstituted alkylgroup 1 to 10, a substituted or unsubstituted aralkyl group having 7 to20 carbon atoms, or a substituted or unsubstituted aryl group having 6to 20 carbon atoms; or R¹² and R¹³, and R¹⁹ and R²⁰, each independently,are linked together and represent cyclic structure, R¹⁰, R¹¹, R¹⁵, R¹⁶,R²¹ and R²² each independently represents a hydrogen atom, a substitutedor unsubstituted alkyl group having 1 to 10 carbon atom(s), asubstituted or unsubstituted aralkyl group having 7 to 20 carbon atoms,or a substituted or unsubstituted aryl group having 6 to 20 carbonatoms; R¹⁷ and R¹⁸ are the same or different, and represent, a hydrogenatom, a halogen atom, a substituted or unsubstituted alkyl group having1 to 10 carbon atom(s), a substituted or unsubstituted aralkyl grouphaving 7 to 20 carbon atoms, or a substituted or unsubstituted arylgroup having 6 to 20 carbon atoms; and m represents an integer of 0or
 1. 2. The phosphine compound according to claim 1, wherein A¹represents a nitrogen atom and A² represents an oxygen group.
 3. Thephosphine compound according to claim 1, wherein G¹ represents ahydrogen atom.
 4. The phosphine compound according to claim 1, whereinG² is G²¹.
 5. The phosphine compound according to claim 1, wherein G² isG²².
 6. The phosphine compound according to claim 1, wherein G² is G²³.7. The phosphine compound according to claim 1, wherein G² is G²⁴. 8.The phosphine compound according to claim 1, wherein G² is G²⁵.
 9. Thephosphine compound according to claim 1, wherein G² is G²⁶.
 10. Thephosphine compound according to claim 1 wherein G¹ is a protective groupof the hydroxyl group.
 11. The phosphine compound according to claim 10,wherein G¹ is a protective group of the hydroxyl group selected from analkyl group having a secondary or tertiary carbon atom linked to anoxygen atom of phenol, or a C1 to C2 alkyl group substituted with asubstituted or unsubstituted alkoxy group.
 12. The phosphine compoundaccording to claim 10, wherein G¹ is a methoxymethyl group, anethoxyethyl group, a methoxyethoxymethyl group, atrimethylsilylethoxymethyl group or a 1-ethoxyethyl group.
 13. Thephosphine compound according to claim 10, wherein G² is G²¹.
 14. Thephosphine compound according to claim 10 or a Bronsted acid saltthereof, wherein G² is G²².
 15. The phosphine compound according toclaim 10 or a Bronsted acid salt thereof, wherein G² is G²³.
 16. Thephosphine compound according to claim 10, wherein G² is G²⁴.
 17. Thephosphine compound according to claim 10, wherein G² is G²⁵.
 18. Thephosphine compound according to claim 10 or a Bronsted acid saltthereof, wherein G² is G²⁶.
 19. The compound according to claim 1,wherein R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R²⁰ aresubstituted or unsubstituted alkyl groups having 1 to 10 carbon atom(s).20. A production method of a phosphine compound of formula 21B:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R²¹, G¹⁰ and A¹ are the sameas described below, which comprise reacting a phosphine carbonylcompound of formula (21C):

wherein G¹⁰ represents a hydrogen atom or a protective group of thehydroxyl group selected from alkyl groups having a secondary or tertiarycarbon atom linked to an oxygen atom of phenol or a C1 to C2 alkyl groupsubstituted with a substituted or unsubstituted alkoxy group, A¹represents an element of Group 15 of the periodic table; R¹, R², R³, R⁴,R⁶ and R¹ are the same or different and each independently represents ahydrogen atom, a halogen atom, a substituted or unsubstituted alkylgroup having 1 to 10 carbon atom(s), a substituted or unsubstitutedaralkyl group having 7 to 20 carbon atoms, a substituted orunsubstituted aryl group having 6 to 20 carbon atoms, a silyl groupsubstituted with a substituted or unsubstituted hydrocarbon having 1 to20 carbon atom(s), a substituted or unsubstituted alkoxy group having 1to 10 carbon atom(s), a substituted or unsubstituted aralkyloxy grouphaving 7 to 20 carbon atoms, a substituted or unsubstituted aryloxygroup having 6 to 20 carbon atoms, or an amino group disubstituted withhydrocarbons having 1 to 20 carbon atom(s); R⁵ represents, a hydrogenatom, a fluorine atom, a substituted or unsubstituted alkyl group having1 to 10 carbon atom(s), a substituted or unsubstituted aralkyl grouphaving 7 to 20 carbon atoms, a substituted or unsubstituted aryl grouphaving 6 to 20 carbon atoms, or a silyl group substituted with asubstituted or unsubstituted hydrocarbon having 1 to 20 carbon atom(s);R²¹ represents, a substituted or unsubstituted alkyl group having 1 to10 carbon atom(s), a substituted or unsubstituted aralkyl group having 7to 20 carbon atoms, or a substituted or unsubstituted aryl group having6 to 20 carbon atoms, with an organic compound of formula (21F):R⁹NH₂  (21F) wherein R⁹ represents a substituted or unsubstituted alkylgroup having 1 to 10 carbon atom(s), a substituted or unsubstitutedaralkyl group having 7 to 20 carbon atoms, a substituted orunsubstituted aryl group having 6 to 20 carbon atoms, or a group offormula:R⁹⁰—N—R⁹¹; wherein R⁹⁰ and R⁹¹ are the same or different and represent asubstituted or unsubstituted alkyl group having 1 to 10 carbon atom(s),a substituted or unsubstituted aralkyl group having 7 to 20 carbonatoms, or a substituted or unsubstituted aryl group having 6 to 20carbon atoms, or a cyclic structure being linked together.
 21. Theproduction method according to claim 20, wherein G¹⁰ is a protectivegroup of the hydroxyl group selected from alkyl groups having asecondary or tertiary alkyl groups linked to an oxygen atom of phenol,and a C1 to C2 alkyl group substituted with a substituted orunsubstituted alkoxy group.
 22. A production method of a phosphinecompound of formula (21A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R²¹ are as defined inclaim 20, which comprises reacting the phosphine compound (21B) asdefined in claim 20 with an acid.
 23. The production method according toclaim 22, wherein the acid is hydrochloric acid.
 24. A production methodof a phosphine compound of formula (22A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², R¹³, and A¹ arethe same as described below, which comprises reacting a phosphinecompound of formula (22B):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², and R¹³ areas defined in claim 1, and G¹¹ represents a protective group of thehydroxyl group selected from alkyl groups having secondary or tertiaryalkyl groups linked to an oxygen atom of phenol, or a C1 to C2 alkylgroup substituted with a substituted or unsubstituted alkoxy group, withan acid.
 25. The production method according to claim 24, wherein theacid is hydrochloric acid.
 26. A production method of the phosphinecompound of formula (22B) as defined in claim 24, which comprisesreacting a phosphine dihalide of formula (22C):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², R¹³, and A¹ are as defined inclaim 24, with a metal aryl compound of formula (22D):

wherein R¹, R², R³, R⁴ and G¹¹ are as defined in claim 24, and Drepresents an alkali metal or J-X³: wherein J represents an alkalineearth metal, and X³ represents a halogen atom.
 27. A production methodof the compound of formula (22B) as defined in claim 24, which comprisesreacting a phosphine halide compound of formula (25C):

wherein R¹, R², R³, R⁴ and G¹¹ are as defined in claim 24 and X²represents a halogen atom, with a compound of formula (22E):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁰, R¹¹, R¹², R¹³, A¹ and D are as defined inclaim
 24. 28. The production method according to claim 24, wherein R⁵ isa hydrogen atom in formula 22B.
 29. A production method of a phosphinecompound of formula (23B):

wherein R¹, R², R², R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, R²¹, A¹ and G¹¹ are asdefined below, which comprise reacting a phosphine compound of formula(23C):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, and R²¹ are as definedin claim 1, and G¹¹ represents a protective group of the hydroxyl groupselected from an alkyl group having secondary or tertiary carbon atomlinked to an oxygen atom of phenol, or a C1 to C2 alkyl groupsubstituted with a substituted or unsubstituted alkoxy group, with ametal hydride compound.
 30. A production method of a phosphine compoundof formula (23A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴, A¹ and R²¹ are as definedbelow, which comprises reacting the phosphine compound of formula (23B)as defined in claim 29 with an acid.
 31. A production method of aphosphine compound of formula (24A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, and A² are as definedin claim 1, which comprises reacting the phosphine compound of formula(24B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, and A² are the same asdescribed above, and G¹¹ represents a protective group of the hydroxylgroup selected from alkyl groups having secondary or tertiary carbonatom linked to an oxygen atom of phenol, or a C1 to C2 alkyl groupssubstituted with a substituted or unsubstituted alkoxy group, with anacid.
 32. A production method of a phosphine compound of formula (24B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁵, R¹⁶, and A² are as definedbelow, which comprises reacting a phosphine compound of formula (24C):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R¹⁵ are as defined in claim1, G¹¹ represents a protective group of the hydroxyl group selected froman alkyl group having secondary or tertiary carbon atom linked to anoxygen atom of phenol, or a C1 to C2 alkyl group substituted with asubstituted or unsubstituted alkoxy group, and A² represents an elementof Group 16 of the periodic table, with a metal hydride compound or ametal aryl compound of formula (24D):R¹⁶—Y  (24D) wherein R¹⁶ is as defined in claim 1, and Y represents analkali metal or J-X³: wherein J represents an alkaline earth metal, andX³ represents a halogen atom.
 33. The production method according toclaim 32, wherein G¹¹ represents a protective group of the hydroxylgroup selected from alkyl groups having secondary or tertiary carbonatom linked to an oxygen atom of phenol, or a C1 to C2 alkyl groupssubstituted with a substituted or unsubstituted alkoxy group, and A²represents an oxygen atom.
 34. A production method of a phosphinecompound of formula (25A):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸ and m are as defined inclaim 1, which comprises reacting the phosphine compound of formula(25B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸ and m are as definedabove, and G¹¹ represents a protective group of the hydroxyl groupselected from alkyl groups having secondary or tertiary carbon atomlinked to an oxygen atom of phenol, or a C1 to C2 alkyl groupsubstituted with a substituted or unsubstituted alkoxy group, with anacid.
 35. A production method of a phosphine compound of formula (25B)as defined in claim 34, which comprises reacting a phosphine halidecompound of formula (25C):

wherein R¹, R², R³, R⁴ and G¹¹ are as defined in claim 34, and X²represents a halogen atom, with a metal aryl compound of formula (25D):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸ and m are as defined in claim 34, and Drepresents an alkali metal or J-X³, wherein J represents an alkalineearth metal, and X³ represents a halogen atom.
 36. A production methodof the phosphine compound of formula (25B) as defined claim 1, whichcomprises reacting a halophosphine compound of formula (25E)

wherein R⁵, R⁶, R⁷, R⁸, R¹⁷, R¹⁸, and m, and X² represents a halogenatom, with a metal aryl compound of formula (25F):

wherein R¹, R², R³ and R⁴ are as defined in claim 1, and G¹¹ representsa protective group of the hydroxyl group selected from an alkyl grouphaving secondary or tertiary carbon atom linked to an oxygen atom ofphenol, or a C1 to C2 alkyl group substituted with a substituted orunsubstituted alkoxy group and D represents an alkali metal or J-X³,wherein J represents an alkaline earth metal, and X³ represents ahalogen atom.
 37. A production method of a phosphine compound of formula(26A):

wherein A¹, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁹ and R²⁰ are as definedbelow, which comprises reacting a phosphine compound of formula (26B):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and A¹ are as definedin claim 1, and G¹¹ represents a protective group of the hydroxyl groupselected from alkyl groups having secondary or tertiary carbon atomlinked to an oxygen atom of phenol, or a C1 to C2 alkyl groupsubstituted with a substituted or unsubstituted alkoxy group, with anacid.
 38. A production method of the phosphine compound of formula (26B)as defined in claim 37, which comprises reacting a halophosphinecompound of formula (26C):

wherein R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and A¹ are as defined in claim 37, andX² represents a halogen atom, with a metal aryl compound of formula(26D):

wherein R¹, R², R³, R⁴ and G¹¹ are the same as those described in claim37, and D represents an alkali metal or J-X³, wherein J represents analkaline earth metal, and X³ represents a halogen atom.
 39. A productionmethod of a phosphine compound of formula (26B) as defined in claim 38,which comprises reacting an aryl-halogenated phosphorous compound offormula (26E):

wherein R¹, R², R³, R⁴ and G¹¹ are as defined in claim 38, and X²represents a halogen atom, with a metal aryl compound of formula (26F):

wherein A¹, R⁵, R⁶, R⁷, R⁸, R¹⁹, R²⁰ and D are as defined in claim 38.